JP2008276175A - Optical guiding member, optical waveguide and light guide plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical material that excels in heat resistance, light stability, film forming property, adhesion to substratum and adhesion onto layered surface, and that even if used for a prolonged period of time, is free from cracking, peeling or coloring. <P>SOLUTION: The optical member is formed by laminating two or more layers 5, 6, 7 with different refractive indices, wherein at least two layers which are in contact with each other among the layers 5, 6, 7 satisfy the conditions: (1) in the solid Si-nuclear magnetic resonance spectrum, the position and half-width value of peak top is specified. (2) The silicon content be 10 wt.% or higher. (3) The silanol content be in the range of 0.01-10 wt.%. (4) The value of hardness (Shore A) measured by type-A durometer be in the range of 5-90. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel optical member, an optical waveguide, and a light guide plate. Specifically, the present invention relates to an optical member, an optical waveguide, and a light guide plate that are excellent in heat resistance, light resistance, film formability, adhesion to a substrate, and adhesion on a laminated surface.

In recent years, there has been remarkable progress in optical communication systems. Especially in optical waveguides for transmitting optical signals, which are used in optical transceiver modules, further development of high-productivity, low-cost and high-quality materials has been made. It is desired. Also, in so-called optical equipment, for example, when displaying a display unit of a display device such as a display, a button part of a facsimile, a telephone, a cellular phone, and other various household appliances, light that is emitted from a light source is emitted at a desired part. The demand level of high quality is also increasing in the optical plate.
For example, Cited Document 1 uses a siloxane polymer having a specific weight-average molecular weight and number-average molecular weight for the purpose of providing an optical waveguide with less occurrence of cracks and excellent environmental reliability such as temperature cycle. An invention of an optical waveguide is disclosed.

On the other hand, a semiconductor light emitting device member having a specific structure and physical properties and having high durability against ultraviolet rays and heat has been disclosed in the field of semiconductor light emitting device materials different from those of optical waveguides and light guide plates. Reference 2).
JP 2004-91579 A International Publication No. 2006/090804 Pamphlet

  However, the conventional optical member including the cited document 1 is hard and fragile, and thus there are problems such as occurrence of cracks when the film is thickened or a coating is applied to a complicated substrate. Moreover, since the conventional optical member does not have sufficient adhesion to a substrate or a film material to be laminated for the purpose of moisture prevention, there has been a problem of coating film peeling. Moreover, in the conventional optical member, since the adhesiveness in the lamination | stacking surface is not enough when the layer from which a material differs is laminated | stacked, there existed the subject of coating film peeling. Furthermore, heat resistance and light resistance that can be applied to long-term use have been desired for optical members.

  On the other hand, the applicability to optical members used as laminates such as optical waveguides and light guide plates is not predictable, and in particular, the problem of coating film peeling due to insufficient adhesion on the laminated surface can be solved. It has been common technical knowledge of those skilled in the art that it is difficult to divert a general compound because it is difficult. Furthermore, there was no special technical motive that could immediately use the semiconductor light-emitting device member of Patent Document 2.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is excellent in heat resistance, light resistance, film formability, adhesion to a substrate or film material, and adhesion on a laminated surface, and causes cracking, peeling and coloring even after long-term use. It is to provide an optical member that does not occur.

  As a result of intensive studies to achieve the above object, the present inventors have a specific peak in a solid Si-nuclear magnetic resonance (hereinafter referred to as “NMR” as appropriate) spectrum and contain silicon. Polymers with a rate greater than or equal to a specific value and a silanol content within a predetermined range have a high degree of freedom in thick film design, and cracks are suppressed even in the thick film part, and peeling from the substrate, film material, etc. Further, the inventors have found that peeling on the laminated surface is suppressed, and that the heat resistance and light resistance are excellent, and the present invention has been completed.

That is, the gist of the present invention resides in an optical member, an optical waveguide, and a light guide plate having the following features [1] to [13].
[1] An optical member in which two or more layers having different refractive indexes are laminated, and at least two layers in contact with each other satisfy the following condition (hereinafter referred to as “ It may be referred to as “first optical member of the present invention”).
(1) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.
(4) Hardness measurement value (Shore A) by durometer type A is 5 or more and 90 or less.

[2] An optical member formed by laminating two or more layers having different refractive indexes, wherein at least two layers in contact with each other satisfy the following condition (hereinafter referred to as “ It may be referred to as “the second optical member of the present invention”).
(5) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.5 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 1.0 ppm to 5.0 ppm. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.

[3] The optical material according to [1] or [2], wherein a refractive index of at least one of the layers in contact with each other is 1.45 or more.
[4] The refractive index of at least one of the layers in contact with each other is 1.45 or more, and the refractive index of at least one other layer is less than 1.45. Optical material.

[5] An optical member formed by laminating two or more layers having different haze values, wherein at least two layers in contact with each other satisfy the following condition (hereinafter referred to as “ It may be referred to as “the third optical member of the present invention”).
(1) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.
(4) Hardness measurement value (Shore A) by durometer type A is 5 or more and 90 or less.

[6] An optical member formed by laminating two or more layers having different haze values, wherein at least two layers in contact with each other satisfy the following condition (hereinafter referred to as “ It may be referred to as “the fourth optical member of the present invention”).
(5) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.5 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 1.0 ppm to 5.0 ppm. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.

[7] The optical member according to [5] or [6], wherein at least one of the layers in contact with each other has a haze value of 50 or more.
[8] The optical member according to any one of [1] to [7], wherein at least one of the layers in contact with each other contains inorganic particles.
[9] The optical member according to [8], wherein the inorganic particles have a median particle diameter of 1 to 10 nm.

[10] At least one of the layers contacting each other contains inorganic particles having a median particle size of 0.05 to 50 μm, and the layer and / or at least one other layer is an inorganic particle having a median particle size of 1 to 10 nm. The optical member according to any one of [5] to [7], comprising:
[11] The optical member according to any one of [1] to [10], wherein at least one of the layers in contact with each other contains a phosphor.
[12] The optical member according to any one of [1] to [11], wherein an angle formed between the side surface and the laminated surface of the optical member is 30 degrees or greater and 80 degrees or less.
[13] The optical member according to any one of [1] to [12], further including a boundary portion penetrating at least two of the layers in contact with each other.
[14] An optical waveguide formed using the optical member according to any one of [1] to [13].
[15] A light guide plate formed using the optical member according to any one of [1] to [13].

  In the following description, when referring to the first to fourth optical members of the present invention without distinction, they are simply referred to as “optical members of the present invention”.

The optical member of the present invention has a high degree of freedom in film thickness design, the occurrence of cracks in the thick film part is suppressed, the peeling from the substrate and the peeling on the laminated surface are suppressed, and further excellent in heat resistance and light resistance. Has the effect.
The optical waveguide and light guide plate formed using the optical member of the present invention have a high degree of freedom in designing the film thickness, and the occurrence of cracks is suppressed even in the thick film part, and peeling from the substrate and peeling on the laminated surface are prevented. It is suppressed and has an effect of being excellent in heat resistance and light resistance.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

[1] Characteristics of layers constituting optical member The optical member of the present invention is characterized in that two or more layers are laminated. In the optical member of the present invention, at least two layers in contact with each other among the stacked layers have the characteristics shown below. Among these, it is preferable that all of the stacked layers have the following characteristics.

That is, in the first and third optical members of the present invention, at least two layers in contact with each other among the layers constituting the optical member have the following characteristics (1) to (4).
Characteristic (1) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
Characteristic (2) The silicon content is 10% by weight or more.
Characteristic (3) Silanol content is 0.01 wt% or more and 10 wt% or less.
Characteristic (4) Hardness measurement value (Shore A) by durometer type A is 5 or more and 90 or less.

Of the layers constituting the second and fourth optical members of the present invention, at least two layers in contact with each other have the above-mentioned characteristics (2) (3) and the following characteristics (5).
Characteristic (5) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.5 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 1.0 ppm to 5.0 ppm. .

  Hereinafter, of the layers constituting the first to fourth optical members of the present invention, focusing on these characteristics (1) to (5), the layer having the above characteristics (hereinafter simply referred to as “specific layer” as appropriate). ").) Will be described.

[1-1] Characteristics (1) and (5): Solid Si-nuclear magnetic resonance spectrum The specific layer according to the present invention satisfies the above characteristics (1) or (5). That is, the specific layer according to the present invention is formed of a material that satisfies the above characteristic (1) or (5). These materials are usually a compound containing silicon as a main component or a composition containing the compound.
A compound containing silicon as a main component is represented by the SiO ₂ · nH ₂ O formula, but structurally, oxygen atoms O are bonded to each vertex of a tetrahedron of silicon atoms Si, and these oxygens It has a structure in which silicon atom Si is further bonded to atom O and spreads in a net shape. The schematic diagram shown below represents the Si—O net structure while ignoring the tetrahedral structure, and in the repeating unit of Si—O—Si—O—, one oxygen atom O is represented. Some are substituted with other members (for example, —H, —CH _3, etc.), and when attention is paid to one silicon atom Si, as shown in (A) of the schematic diagram, four —OSi are silicon atoms having Si (Q ^4), a silicon atom Si (Q ³⁾ having three -OSi as shown in the schematic diagram (B) or the like is present. In the solid Si-nuclear magnetic resonance spectrum (solid Si-NMR spectrum) measurement, the peaks based on the silicon atoms Si are sequentially called Q ⁴ peak, Q ³ peak,.

These silicon atoms having four bonded oxygen atoms are generally referred to as Q sites. In the present invention, Q ^{0 to} Q ⁴ peaks derived from the Q site are referred to as a Q ⁿ peak group. The Q ⁿ peak group of the silica film containing no organic substituent is usually observed as a multimodal peak continuous in the region of chemical shift of −80 to −130 ppm.
In contrast, silicon atoms to which three oxygen atoms are bonded and other atoms (usually carbon) are bonded are generally referred to as T sites. The peak derived from the T site is observed as each peak of T ^{0 to} T ³ as in the case of the Q site. In the present invention, each peak derived from the T site is referred to as a T ⁿ peak group. The T ⁿ peak group is generally observed as a multimodal peak continuous in the region on the higher magnetic field side (usually −80 to −40 ppm) than the Q ⁿ peak group.

Furthermore, a silicon atom to which two oxygen atoms are bonded and two other atoms (usually carbon) are bonded is generally referred to as a D site. Similarly to the peak group derived from the Q site and the T site, the peak derived from the D site is also observed as each peak of D ^{0 to} D ⁿ (D ⁿ peak group), which is further than the peak group of Q ⁿ and T ^n. It is observed as a multimodal peak in the region on the high magnetic field side (usually the region with a chemical shift of 0 to −40 ppm). The ratio of the area of each peak group of D ⁿ , T ⁿ , and Q ⁿ is equal to the molar ratio of silicon atoms placed in the environment corresponding to each peak group. In terms of the molar amount, the total area of the D ⁿ peak group and the T ⁿ peak group usually corresponds to the molar amount of all silicon directly bonded to the carbon atom.

Bond When measuring the solid Si-NMR spectrum of a particular layer of the optical member of the present invention, the D ⁿ peak group and T ⁿ peak group originating from silicon atoms in which carbon atoms directly bonded organic group, and the carbon atom of an organic group ^Qn peaks derived from silicon atoms that are not present appear in different regions. Among these peaks, the peak of less than −80 ppm corresponds to the Q ⁿ peak as described above, and the peaks of −80 ppm or more correspond to the D ⁿ and T ⁿ peaks. Although the Q ⁿ peak is not essential in the specific layer, at least one, preferably a plurality of peaks are observed in the D ⁿ and T ⁿ peak regions.

  In addition, the value of the chemical shift of a specific layer can be calculated based on the result of performing solid Si-NMR measurement using the method mentioned later in description of an Example, for example. In addition, analysis of measurement data (half-width or silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.

In the optical member of the present invention, the specific layer cures densely without causing cracks even in the thick film portion, and obtains a cured product that is excellent in adhesion to the substrate and the laminated surface between each layer and excellent in durability against light and heat. The reason why the above-described characteristic (1) or (5) is desirable in exhibiting the excellent characteristic that it can be performed is not clear, but is presumed as follows.
As a method for obtaining an optical member made of inorganic glass, a melting method in which low-melting glass is melted and sealed, and a sol-gel that applies a solution obtained by hydrolysis and polycondensation of alkoxysilane or the like at a relatively low temperature, and is dried and cured. There is a law. Of these members, only the ^Qn peak is mainly observed for the member obtained from the melting method, but it requires a high temperature of at least 350 ° C. for melting and is not a practical method because the optical member is thermally deteriorated.

On the other hand, the hydrolysis / polycondensation product obtained from the tetrafunctional silane compound in the sol-gel method becomes a completely inorganic glass and is extremely excellent in heat resistance and weather resistance, but the curing reaction is silanol condensation (dehydration / dehydration). Since the crosslinking proceeds due to the (alcohol) reaction, the dehydration occurs, resulting in weight reduction and volume shrinkage. Therefore, ^{if the} raw material is composed of only tetrafunctional silane having a Q ⁿ peak, the degree of curing shrinkage becomes too large, and the film tends to crack and cannot be thickened. In such a system, attempts are made to increase the film thickness by adding inorganic particles as an aggregate or by overcoating, but generally the limit film thickness is about 10 μm. When sol-gel glass is used as an optical member, there is a problem that a sufficient film thickness must be ensured in order to coat a substrate having a complicated shape. In addition, as described above, in order to sufficiently reduce the residual silanol and obtain a completely inorganic glass, heating at a high temperature of 400 ° C. or more is required, and the peripheral members including the substrate are thermally deteriorated, which is not realistic. It was.

In contrast, in the optical member of the present invention, in a particular layer, by adjusting the crosslink density, in order to give flexibility to the film, bifunctional with trifunctional silanes and / or D ⁿ peak with T ⁿ peak By introducing silane and carrying out hydrolysis and polycondensation at the same time, the volume reduction due to dehydration condensation and the crosslinking density can be appropriately reduced within the range that does not hinder the function, and the hydrolysis / condensation process and the drying process are controlled. Thus, a transparent glass film-like member having a film thickness of 1000 μm can be obtained. Therefore, in the present invention, the presence of a T ⁿ peak and / or a D ⁿ peak observed at −80 ppm or more is essential.

As a method for thickening a bifunctional or trifunctional raw material as a main component in this manner, for example, a technique of a hard coat film such as glasses is known, but the film thickness is several μm or less. Since these hard coat films are thin, solvent volatilization is easy and uniform curing is possible, and differences in adhesion to the substrate and linear expansion coefficient have been the main cause of cracks. On the other hand, since the optical member of the present invention having flexibility has a film thickness as large as that of a paint, the film itself has a certain degree of strength, and a slight difference in coefficient of linear expansion can be absorbed. If such a film does not have flexibility, the generation of internal stress different from the case of a thin film becomes a new problem due to volume reduction by solvent drying. In other words, when molding into a deep container with a small opening area such as an LED cup, if heat curing is performed in a state where drying at the deep part of the film is insufficient, solvent volatilization occurs after cross-linking and the volume is reduced, resulting in large cracks. It causes rough surfaces such as foam, yuzu skin. A large internal stress is applied to such a film. When solid-state Si-NMR of this film is measured, the detected D ⁿ , T ⁿ , and Q ⁿ peak groups have a siloxane bond angle as compared with a case where the internal stress is small. A distribution is produced, each with a broader peak. This fact means that the bond angle represented by two -OSi with respect to Si has a large strain. That is, even with a film made of the same raw material, as the specific layer in the optical member of the present invention, the narrower the half-value width of these peaks, the less likely to crack, and the higher the quality film.

It should be noted that the phenomenon in which the half-value width increases in accordance with the strain is observed more sensitively as the degree of restraint of the molecular motion of the Si atoms increases, and the ease of appearing becomes D ⁿ <T ⁿ <Q ⁿ .
In the present invention, the half-value width of the peak observed in the region of −80 ppm or more is characterized by being smaller (narrower) than the half-value width range of the optical member known so far by the sol-gel method.

When arranged for each chemical shift, in the first and third optical members of the present invention, the half width of the T ⁿ peak group observed at a peak top position of −80 ppm or more and less than −40 ppm is usually 5.0 ppm or less. Preferably it is 4.0 ppm or less, and is 0.3 ppm or more normally, Preferably it is the range of 0.5 ppm or more (characteristic (1)).
In the second and fourth optical members of the present invention, the half width of the T ⁿ peak group observed at a peak top position of −80 ppm or more and less than −40 ppm is usually 5.0 ppm or less, preferably 4.0 ppm. Hereinafter, it is usually 1.0 ppm or more, preferably 1.5 ppm or more (characteristic (5)).

Similarly, in the first and third optical members of the present invention, the full width at half maximum of the D ⁿ peak group observed at the peak top position of −40 ppm or more and 0 ppm or less is generally T ^It is smaller than in the case of the ⁿ peak group, and is usually 3.0 ppm or less, preferably 2.0 ppm or less, and usually 0.3 ppm or more (characteristic (1)).
In the second and fourth optical members of the present invention, the half width of the D ⁿ peak group observed at the peak top position of −40 ppm or more and 0 ppm or less is generally T ⁿ because the molecular motion constraint is small. It is smaller than the peak group, and is usually 3.0 ppm or less, preferably 2.0 ppm or less, and usually 0.5 ppm or more (characteristic (5)).

  If the half-value width of the peak observed in the chemical shift region is larger than the above range, the molecular motion is constrained and the strain is large, and cracks and peeling from the coated substrate are likely to occur. There is a possibility that it becomes a member inferior in performance. For example, in the case where a large amount of tetrafunctional silane is used, or in the state where rapid drying is performed in the drying process and a large internal stress is stored, the full width at half maximum is larger than the above range.

In addition, when the half width of the peak is smaller than the above range, Si atoms in the environment are not involved in siloxane crosslinking. For example, the crosslinked portion is formed by Si—C bonds like a silicone resin, and the dimethylsiloxane chain There is a possibility that the member is inferior in heat resistance and weather resistance compared to a substance formed mainly of a siloxane bond, such as an example in which only the D ² peak is observed or an example in which trifunctional silane remains in an uncrosslinked state.

Furthermore, as described above, in the solid Si-nuclear magnetic resonance spectrum of the specific layer of the optical member of the present invention, at least one, preferably a plurality of peaks are observed in the D ⁿ and T ⁿ peak regions. Thus, the solid Si- NMR spectrum specific layer of the optical member of the present invention, a peak selected from the group consisting of D ⁿ peak group and T ⁿ peak group having a FWHM ranging as described above, at least one, It is desirable to have two or more.

[1-2] Property (2): Silicon Content The specific layer of the optical member of the present invention must have a silicon content of 10% by weight or more (characteristic (2)). That is, the specific layer according to the present invention must have a silicon content of 10% by weight or more of the material forming the specific layer.
The basic skeleton of the specific layer of the optical member of the present invention is the same inorganic siloxane bond as glass (silicate glass). As is apparent from the chemical bond comparison table shown in Table 1 below, this siloxane bond has the following characteristics excellent as an optical member.
(I) Since the binding energy is large and thermal decomposition and photolysis are difficult, light resistance is good.
(II) It is slightly polarized electrically.
(III) The degree of freedom of the chain structure is large, a structure with high flexibility is possible, and the chain structure can freely rotate around the center of the siloxane chain.
(IV) The degree of oxidation is large and no further oxidation occurs.
(V) Rich in electrical insulation.

  Because of these characteristics, the specific layer, which is a silicone-based layer formed of a skeleton in which siloxane bonds are bonded three-dimensionally and with a high degree of cross-linking, is different from layers using other materials such as epoxy resin in glass or rock. It can be understood that the protective film is close to inorganic materials such as heat resistance and light resistance. In particular, a specific layer having a methyl group as a substituent does not absorb in the ultraviolet region, so that photodegradation is unlikely to occur and is excellent in light resistance.

The silicon content of the specific layer of the optical member of the present invention is 10% by weight or more as described above. However, when the high refractive index is not required, it is not necessary to contain a component necessary for increasing the refractive index. Therefore, it is usually 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO ₂ is 47% by weight.

  The silicon content of the specific layer of the optical member of the present invention is analyzed by, for example, inductively coupled plasma spectroscopy (hereinafter, abbreviated as “ICP” as appropriate) using a method described later in the description of the examples. And can be calculated based on the result.

[Measurement of silicon content]
A single cured product of the specific layer of the optical member is pulverized to about 100 μm, fired in a platinum crucible in air at 450 ° C. for 1 hour, then 750 ° C. for 1 hour, and 950 ° C. for 1.5 hours. After removing the carbon component, add 10 times or more amount of sodium carbonate to a small amount of the obtained residue, heat it with a burner and melt it, cool it, add demineralized water, and adjust the pH to neutral with hydrochloric acid. However, the volume is adjusted to about several ppm as silicon, and ICP analysis is performed.

[1-3] Property (3): Silanol content The specific layer of the optical member of the present invention has a silanol content of usually 0.01% by weight or more, preferably 0.1% by weight or more, and more preferably 0.8%. It is in the range of 3% by weight or more, usually 10% by weight or less, preferably 8% by weight or less, more preferably 6% by weight or less (characteristic (3)). That is, in the specific layer according to the present invention, the silanol content of the material forming the specific layer falls within the above range.

  Usually, a glass body obtained by a sol-gel method using alkoxysilane as a raw material does not completely polymerize and become an oxide under mild curing conditions at 150 ° C. for about 3 hours, and a certain amount of silanol remains. A glass body obtained only from tetraalkoxysilane has high hardness and high light resistance, but has a high degree of cross-linking so that the degree of freedom of molecular chains is small, and complete condensation does not occur, so the amount of residual silanol is large. Further, when the hydrolysis / condensation liquid is dry-cured, the viscosity increases quickly due to the large number of cross-linking points, and the drying and curing proceed simultaneously, resulting in a bulk body having a large distortion. When such a member is used as an optical member, new internal stress is generated due to condensation of residual silanol during long-term use, and problems such as cracks, peeling, and disconnection are likely to occur. In addition, the fracture surface of the member has more silanol and less moisture permeability, but it has high surface hygroscopicity and tends to invade moisture. Although the silanol content can be reduced by high-temperature firing at 400 ° C. or higher, the heat resistance of the optical member is almost 260 ° C. or lower, which is not realistic.

  On the other hand, since the optical component of the present invention has a low silanol content in the specific layer, it has little change with time, has excellent long-term performance stability, and has excellent performance with low moisture absorption and moisture permeability. However, since the member or layer containing no silanol is inferior in adhesion to the substrate or adhesion on the laminated surface when the optical member is a laminate, in the present invention, the silanol content is optimal as described above. A range exists.

Since the specific layer of the optical member of the present invention contains an appropriate amount of silanol, the silanol hydrogen bonds to the polar portion present on the substrate or the laminated surface of each layer, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.
In addition, the silanol content of the specific layer of the optical member of the present invention is, for example, measured by solid Si-NMR spectrum using the method described below, and based on the ratio of the peak area derived from silanol to the total peak area, It can be calculated by obtaining the ratio (%) of silicon atoms that are silanols in the interior and comparing it with the separately analyzed silicon content.

  In some cases, the specific layer may contain silanol by adding inorganic particles containing silanol such as aerosil, but the compound that is mainly the matrix layer forming the specific layer is preferably silanol as a part of its skeleton. It is preferable to contain.

[Solid Si-NMR spectrum measurement and silanol content calculation]
When performing a solid Si-NMR spectrum about the specific layer of the optical member of the present invention, first, solid Si-NMR spectrum measurement and data analysis are performed under the following conditions. Next, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Ask for.

The analysis of the measurement data (silanol amount analysis) is performed by a method in which each peak is divided and extracted by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.
[Example of equipment conditions]
Apparatus: Chemmagnetics Infinity CMX-400 Nuclear magnetic resonance spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 Observation width: 30 kHz
Broadening factor: 20Hz

[Data processing example]
For the specific layer of the optical member of the present invention, 512 points are taken as measurement data, and are zero-filled to 8192 points and Fourier transformed.

[Example of waveform separation analysis]
For each peak of the spectrum after Fourier transform, optimization calculation is performed by a non-linear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.
In addition, identification of a peak is AIChE Journal, 44 (5), p. Refer to 1141, 1998, etc.

  Moreover, the silanol content of the specific layer of the optical member of the present invention can be determined by the following IR measurement. Here, although IR measurement is easy to identify the silanol peak, the shape of the peak is broad and an area error is likely to occur, and the procedure is complicated because it is necessary to accurately prepare a sample with a constant film thickness for quantitative work. In order to perform strict quantification, it is preferable to use solid Si-NMR. When measuring the amount of silanol using solid Si-NMR, if the amount of silanol is very small and difficult to detect, if multiple peaks overlap and it is difficult to isolate the silanol peak, When the chemical shift of the silanol peak is unknown, the concentration of silanol can be determined by performing IR measurement complementarily.

[Calculation of silanol content by IR measurement]
・ Fourier Transform Infrared Spectroscopy (Fourier Transform Infrared Spectroscopy)
・ Device: NEXUS670 and Nic-Plan made by Thermo Electron
・ Resolution: 4cm ^-1
・ Total number of times: 64 times ・ Purge: N ₂
Measurement example: A thin film sample having a thickness of 200 μm is coated on a Si wafer, an infrared absorption spectrum is measured for each Si wafer by a transmission method, and the total area of silanol peaks at wave numbers 3751 cm ⁻¹ and 3701 cm ⁻¹ is obtained. On the other hand, trimethylsilanol as a known concentration sample is diluted in anhydrous carbon tetrachloride, an infrared absorption spectrum is measured by a transmission method using a liquid cell having an optical path length of 200 μm, and silanol is compared by comparing the peak area ratio with an actual sample. The concentration can be calculated. In the infrared absorption spectrum, since the peak derived from the sample adsorbed water is detected as the background of the silanol peak, the sample thin film is heated at 150 ° C. for 20 minutes or more at normal pressure before measurement, or 10 minutes at 100 ° C. The adsorbed water is removed by a method such as vacuum treatment.

[1-4] Characteristic (4): Hardness measurement value The hardness measurement value is an index for evaluating the hardness of the specific layer of the optical member of the present invention, and is measured by the following hardness measurement method.
The specific layer of the optical member of the present invention is preferably a member that exhibits an elastomeric shape. That is, the optical member of the present invention uses a plurality of members having different coefficients of thermal expansion in the substrate or each layer, but the specific layer exhibits an elastomeric shape as described above, so that the specific layer and the specific layer are separated. The optical member of the present invention used can relieve stress due to expansion and contraction of each of the above components. Therefore, it is possible to provide an optical member that is less likely to be peeled, cracked, disconnected, etc. during use and that has excellent reflow resistance and temperature cycle resistance.

  Specifically, the specific layer of the optical member of the present invention has a durometer type A hardness measurement value (Shore A) of usually 5 or more, preferably 7 or more, more preferably 10 or more, and usually 90 or less, preferably Is 80 or less, more preferably 70 or less (characteristic (4)). By having a hardness measurement value in the above range, the specific layer and the optical member of the present invention using the specific layer are less prone to cracking, and can have the advantages of excellent reflow resistance and temperature cycle resistance. .

[Hardness measurement method]
The hardness measurement value (Shore A) can be measured by the method described in JIS K6253. Specifically, the measurement can be performed using an A-type rubber hardness meter manufactured by Furusato Seiki Seisakusho.

[1-5] Other physical properties The specific layer of the optical member of the present invention is mainly characterized by the above-mentioned properties, but preferably has the following structure and properties.

[1-5-1] Light Transmittance When the specific layer of the optical member of the present invention is used for a light guide or a light guide plate using a semiconductor light emitting device as a light source, the light emission wavelength of the light source at a film thickness of 1 mm is used. The light transmittance (transmittance) in is usually 80% or more, preferably 85% or more, and more preferably 90% or more. When a specific layer is used as a light-transmitting part in an optical member, if the transparency of the light-transmitting part is low, the luminance of the light source using the light-transmitting part is reduced. It becomes difficult to obtain.

  Here, for example, in the case of a semiconductor light-emitting device, the “light-emitting wavelength of the light source” varies depending on the type of the light-emitting device, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably It refers to a wavelength in the range of 500 nm or less. If the light transmittance at a wavelength in this range is low, the specific layer absorbs light, the light extraction efficiency is lowered, and a high-intensity optical waveguide or light guide plate cannot be obtained. Furthermore, the energy corresponding to the decrease in the light extraction efficiency is changed to heat, which causes thermal deterioration of the optical waveguide or the light guide plate.

In the ultraviolet to blue region (wavelength 300 nm to 500 nm), the optical material is likely to be light-degraded. Therefore, if a specific layer having excellent durability is used for a light source having an emission wavelength in this region, the effect is increased. Therefore, it is preferable.
The light transmittance of the optical material such as the material of the specific layer should be measured with an ultraviolet spectrophotometer using, for example, a sample of a single cured film having a smooth surface molded to a film thickness of 1 mm by the following method. Can do.

(Measurement of transmittance)
Using an ultraviolet spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) with a single cured film having a smooth surface with a thickness of about 1 mm that is not scattered by scratches or unevenness of the optical material, light is emitted at a wavelength of 200 nm to 800 nm. Measure transmittance.

[1-5-2] Peak Area Ratio The specific layer of the optical member of the present invention preferably satisfies the following conditions. That is, the specific layer of the optical member of the present invention has the following characteristics in the solid Si-nuclear magnetic resonance spectrum: (chemical shift—total area of peaks of 40 ppm or more and 0 ppm or less) / (chemical shift—total area of peaks of less than 40 ppm) The ratio (hereinafter referred to as “peak area ratio according to the present invention” as appropriate) is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably 100 or less, more preferably 50 or less. It is preferable that

The peak area ratio according to the present invention is in the above range because the specific layer of the optical member of the present invention has more bifunctional silanes than trifunctional or higher functional silanes such as trifunctional silanes and tetrafunctional silanes. Represents. Thus, by having many bifunctional or less silane, a specific layer can exhibit an elastomer form and can relieve stress.
However, the specific layer may exhibit an elastomeric shape even if it does not satisfy the above-described conditions for the peak area ratio according to the present invention. For example, the case where a specific layer is produced using a coupling agent such as an alkoxide of a metal other than silicon as a crosslinking agent corresponds to this case. The technique for the specific layer to exhibit an elastomeric shape is arbitrary, and is not limited to the above-described conditions for the peak area ratio according to the present invention.

[1-5-3] Functional group The specific layer of the optical member of the present invention has a predetermined functional group (for example, a hydroxyl group, oxygen in a metalloxane bond, etc.) present on the surface of a resin such as polyphthalamide, ceramic or metal. And a functional group capable of hydrogen bonding. The substrate for installing the optical member is usually made of resin, ceramic or metal. Moreover, a hydroxyl group usually exists on the surface of ceramic or metal. On the other hand, the specific layer usually has a functional group capable of hydrogen bonding with the hydroxyl group. Therefore, the optical member of the present invention having the specific layer is excellent in adhesion to the substrate due to the hydrogen bond.

Examples of the functional group that can be hydrogen bonded to the hydroxyl group in the specific layer include silanol and alkoxy group. The functional group may be one type or two or more types.
Since the specific layer of the present invention has these functional groups, it has excellent adhesiveness and can be laminated by recoating. Utilizing this property, it is possible to easily produce an optical member having a light guide function, an optical waveguide, a light guide plate, and the like by laminating two or more layers having adjusted refractive indexes.
In addition, as described above, whether the specific layer has a functional group capable of hydrogen bonding with respect to a hydroxyl group depends on solid Si-NMR, solid ¹ H-NMR, infrared absorption spectrum (IR), Raman, and the like. It can be confirmed by spectroscopic techniques such as spectrum.

[1-5-4] Heat resistance The specific layer of the optical member of the present invention is excellent in heat resistance. That is, even when left under a high temperature condition, the transmittance of light having a predetermined wavelength hardly changes. Specifically, the specific layer has a transmittance maintenance ratio for light having a wavelength of 400 nm before and after being left at 200 ° C. for 500 hours, usually 80% or more, preferably 90% or more, more preferably 95% or more. Further, it is usually 110% or less, preferably 105% or less, more preferably 100% or less.
The variation ratio can be measured by the transmittance measurement using an ultraviolet / visible spectrophotometer in the same manner as the light transmittance measuring method described in [1-5-1].

[1-5-5] UV resistance The specific layer of the optical member of the present invention is excellent in light resistance. That is, even when UV (ultraviolet light) is irradiated, the transmittance with respect to light having a predetermined wavelength is not easily changed. Specifically, the specific layer has a transmittance maintenance factor of light at a wavelength of 400 nm before and after irradiation with light having a center wavelength of 380 nm and a radiation intensity of 0.4 kW / m ² for 72 hours, preferably 80% or more, preferably It is 90% or more, more preferably 95% or more, and usually 110% or less, preferably 105% or less, more preferably 100% or less.
The variation ratio can be measured by the transmittance measurement using an ultraviolet / visible spectrophotometer in the same manner as the light transmittance measuring method described in [1-5-1].

[1-5-6] Residual catalyst amount The specific layer of the optical member of the present invention usually uses an organometallic compound catalyst containing at least one element selected from zirconium, hafnium, tin, zinc, and titanium. Manufactured. Therefore, these catalysts usually remain in the specific layer. Specifically, the specific layer contains the above-mentioned organometallic compound catalyst in terms of metal element, usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.02% by weight or more. The content is usually 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. However, when the oxide particle containing the said metal element is mix | blended in order to adjust the refractive index of a specific layer, the metal element of the quantity exceeding the said range is detected.
The content of the organometallic compound catalyst can be measured by ICP analysis.

[1-5-7] Molecular Weight The specific layer of the optical member of the present invention is in terms of polystyrene measured by GPC (gel permeation chromatography) of the material forming the specific layer (specific layer forming liquid described later). The weight average molecular weight (Mw) is usually 500 or more, preferably 900 or more, more preferably 3200 or more, and usually 400,000 or less, preferably 70,000 or less, more preferably 27,000 or less. If the weight average molecular weight is too small, bubbles tend to be generated at the time of curing after coating the substrate, or liquid leakage may occur from minute gaps between the package and the substrate. There is a tendency that the sticking tendency, the complicated shape on the substrate, and the filling efficiency to the wiring portion are deteriorated.

  The molecular weight distribution (Mw / Mn, where Mw represents a weight average molecular weight and Mn represents a number average molecular weight) is usually 20 or less, preferably 10 or less, more preferably 6 or less. If the molecular weight distribution is too large, the member tends to thicken over time even at low temperatures and the coating efficiency to the substrate tends to deteriorate. In addition, Mn can be measured by polystyrene conversion by GPC like Mw.

  In addition, the specific layer forming liquid of the optical member of the present invention preferably has a low molecular weight component having a specific molecular weight or less. Specifically, the component having a molecular weight of 800 or less in the GPC area ratio in the specific layer forming liquid is usually 10% or less, preferably 7.5% or less, more preferably 5% or less of the whole. If there are too many low molecular weight components, bubbles may be generated at the time of curing after coating the substrate, or the weight yield (solid content ratio) at the time of curing may decrease due to volatilization of the main component.

Furthermore, the specific layer forming liquid of the optical member of the present invention preferably has a small amount of high molecular weight component having a specific molecular weight or more. Specifically, in the GPC analysis value of the specific layer forming liquid, the molecular weight at which the high molecular weight fractionation range is 5% is usually 1000000 or less, preferably 330,000 or less, more preferably 110,000 or less. If there are too many high molecular weight fractions in GPC,
a) The specific layer forming liquid thickens over time even in low-temperature storage,
b) Water is generated by dehydration condensation during storage, and it is easy to peel off from the substrate or package after applying the specific layer.
c) Since the viscosity is high, air bubbles are not easily removed during curing after coating the substrate.
There is a possibility.

In summary, the specific layer forming liquid of the optical member of the present invention is preferably in the molecular weight range shown above, and examples of the method for making such a molecular weight range include the following methods.
(I) The polymerization reaction during the synthesis is sufficiently performed to consume unreacted raw materials.
(Ii) After the synthesis reaction, light boiling components are sufficiently distilled off to remove light boiling low molecular weight residues.
(Iii) The reaction rate and conditions during the synthesis reaction are appropriately controlled so that the polymerization reaction proceeds uniformly, and the molecular weight distribution is not increased more than necessary.

  For example, when a specific layer is formed from a polycondensate obtained by hydrolysis and polycondensation of a specific compound, as in “[2] Manufacturing method of optical member”, hydrolysis / polymerization at the time of synthesizing a specific layer forming liquid It is preferable to proceed the reaction uniformly while maintaining an appropriate reaction rate. Hydrolysis / polymerization is usually carried out in the range of 15 ° C. or higher, preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and usually 140 ° C. or lower, preferably 135 ° C. or lower, more preferably 130 ° C. or lower. The hydrolysis / polymerization time varies depending on the reaction temperature, but is usually 0.1 hour or more, preferably 1 hour or more, more preferably 3 hours or more, and usually 100 hours or less, preferably 20 hours or less, more preferably 15 It is carried out in the range of less than time. If the reaction time is shorter than this, the required molecular weight is not reached, or the reaction proceeds unevenly. As a result, low molecular weight raw materials remain and high molecular weight components exist, resulting in poor cured product quality and poor storage stability. There is a possibility of becoming. On the other hand, if the reaction time is longer than this, the polymerization catalyst may be deactivated or the synthesis may take a long time and the productivity may deteriorate.

If the reaction activity of the raw material is low and the reaction does not proceed easily, for example, an inert gas such as argon gas, helium gas, or nitrogen gas is circulated to accompany moisture or alcohol generated in the condensation reaction. The removal may be performed to accelerate the reaction.
The reaction time is preferably adjusted as appropriate while controlling the molecular weight by GPC and viscosity measurement. Furthermore, it is preferable to adjust in consideration of the temperature rising time.
When using a solvent, it is preferable to carry out the solvent distillation at normal pressure as required. Furthermore, when the boiling point of the solvent or the low molecular weight substance to be removed is the curing start temperature (usually 120 ° C. or higher), it is preferable to perform vacuum distillation if necessary. On the other hand, depending on the purpose of use, such as application of a thin layer of the light guide film, a part of the solvent may remain for lowering the viscosity, or a solvent different from the reaction solvent may be added after the reaction solvent is distilled off.

  Here, it is preferable that the upper limit and the lower limit of the molecular weight distribution of the specific layer forming liquid fall within the above range, and the molecular weight distribution does not necessarily have to be a mountain as long as it is within this range. Also, different molecular weight distribution forming liquids may be mixed depending on the purpose such as function addition, in which case the molecular weight distribution curve may be multimodal. For example, in order to give mechanical strength to a specific layer, a small amount of a low specific molecular weight second specific layer forming liquid containing a large amount of adhesion components is contained in the first specific layer forming liquid finished to a high molecular weight. It corresponds to.

[1-5-8] Low boiling point component The specific layer forming liquid and the specific layer of the optical member of the present invention are chromatographed for a heat generation gas in a range of 40 ° C to 210 ° C in TG-mass (pyrolysis MS chromatogram). It is preferable that the gram integration area is small.
TG-mass is for detecting the specific layer forming liquid and the low boiling point component in the specific layer by raising the temperature of the specific layer forming liquid, but when the chromatogram integrated area is large in the range of 40 ° C to 210 ° C. , Water, solvent, and low-boiling components such as 3- to 5-membered cyclic siloxane are present in the components. In such a case, (i) the amount of low-boiling components increases, and bubbles are generated or bleed out during the curing process, resulting in poor adhesion to the substrate, insufficient curing, and large weight loss during curing. Or (ii) the generation of bubbles or bleed-out due to heat generated during lamp emission or reflow. Therefore, it is preferable that the specific layer forming liquid and the specific layer have few such low-boiling components.

In addition, the measurement of TG-mass can be performed by the following operations under the following measurement conditions.
[TG-mass measurement conditions]
Heating furnace: PY-2010 type made by Frontier Lab. Heating furnace temperature rising program: 40 ° C. → 10 ° C./min→400° C.
Interface temperature: 100 ° C
Sample cup: Platinum size (25 μL)
Sample amount: about 10mg
GC: HP 6890 type Column: Empty column (0.25 mm × 10 m)
Carrier: Helium 1.5mL / min
Inlet temperature: 100 ° C
Split ratio: 1/50
Oven: 150 ° C
MS: JEOL AMII-15 type Measurement method: EI method Ionization voltage: 70 eV
Ionization current: 300 μA
Photomultiplier voltage: 400V
Interface temperature: 150 ° C
Ionization chamber temperature: 200 ° C
Mass range: m / z = 10-400
Scan speed: 500ms

[Measurement method of TG-mass]
The gas component generated from the heated sample is introduced into the gas chromatograph through an empty column, and MS analysis is performed. About 10 mg of the sample solution is put in a platinum cell (cup), and the temperature is raised at 40 ° C. to 400 ° C. and 10 ° C./min under He flow. The specific layer forming liquid is solidified at around 120 ° C. to 150 ° C. and then heated in a solid state.

  Examples of a method for suppressing the amount of the low boiling point component detected by TG-mass in the specific layer to be low include the following methods.

(I) The polymerization reaction is sufficiently performed. That is, by ensuring sufficient reaction temperature and reaction time, unreacted light boiling raw materials are consumed, and unreacted terminals that produce water and alcohol during curing are reduced to an appropriate amount. For example, when a specific layer is formed from a polycondensate obtained by hydrolysis and polycondensation of a specific compound, such as “[2] Manufacturing method of optical member” described later, hydrolysis and polycondensation are performed at normal pressure. When it is carried out, the hydrolysis / polycondensation is usually carried out in the range of 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 135 ° C or lower, more preferably 130 ° C or lower. . The hydrolysis / polycondensation reaction time varies depending on the reaction temperature, but is usually 0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, Preferably, it is carried out for 15 hours or less. The reaction time is preferably adjusted as appropriate while sequentially controlling the molecular weight by GPC and viscosity measurement. Furthermore, it is preferable to adjust in consideration of the temperature rising time.

(Ii) When the specific layer forming liquid contains a light boiling component that is not consumed by the reaction, such as a solvent or a low molecular weight cyclic siloxane, unnecessary polymerization at a temperature lower than the curing start temperature during the synthesis of the specific layer forming liquid. Suppresses natural distillation, accompanied by removal of light-boiling substances by circulation of inert gas such as argon gas, nitrogen gas, helium gas, etc., if necessary, distilled under reduced pressure, and the boiling point at normal pressure is about room temperature to about 260 ° C It is preferable to remove the low boiling point component. Specifically, for example, the temperature condition for distilling off the solvent is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 150 ° C. or lower, preferably 130 ° C. or lower. Preferably it shall be 120 degrees C or less. In addition, you may perform the removal of an unnecessary light boiling thing in the separate raw material before a synthesis | combination.

[I-6] Other layer The optical member of the present invention may have a layer other than the specific layer as long as at least two of the layers of the optical member have the specific layer. . A publicly known layer can be arbitrarily applied as a layer other than the specific layer. Further, only one layer other than the specific layer may be provided, or two or more layers may be provided.
However, in order to obtain the effects of the present invention more remarkably, it is preferable that more of the layers of the optical member of the present invention have the characteristics as the specific layer, and all the layers have the above-described characteristics. It is more preferable to have the characteristics as a specific layer.

[2] Method for Manufacturing Optical Member The method for manufacturing the optical member of the present invention is not particularly limited. Therefore, each layer constituting the optical member of the present invention can be produced by any method. Among these, the specific layer is obtained by, for example, hydrolyzing / polycondensing a compound represented by the following general formula (1) or general formula (2) and / or an oligomer thereof to obtain a polycondensate (hydrolysis / polycondensate). Can be obtained by drying. However, since it is preferable that the specific layer is mainly composed of siloxane bonds, it is desirable that the compound represented by the general formula (1) or an oligomer thereof is mainly composed of the raw material. Further, when the hydrolysis / polycondensation product contains a solvent, the solvent may be distilled off in advance before drying.

In the following description, the hydrolysis / polycondensation product or a composition containing the hydrolysis / polycondensation product obtained before the drying step is referred to as a specific layer forming liquid. Therefore, when the specific layer of the optical member of the present invention is manufactured by the manufacturing method described here (hereinafter, referred to as “the manufacturing method of the present invention” as appropriate), what is obtained from this specific layer forming liquid through a drying step It becomes a specific layer.
Hereinafter, the manufacturing method of this specific layer is demonstrated in detail.

[2-1] Raw Material As the raw material, a compound represented by the following general formula (1) (hereinafter referred to as “compound (1)” as appropriate) and / or an oligomer thereof are used.

M ^{m +} X _n Y ¹ _mn (1)

In general formula (1), M is at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, silicon is preferable.
In general formula (1), m represents the valence of M, and is an integer of 1 or more and 4 or less. “M +” represents that it is a positive valence.
n represents the number of X groups and is an integer of 1 or more and 4 or less. However, m ≧ n.

  In general formula (1), X is a hydrolyzable group that is hydrolyzed by water in solution or moisture in the air to produce a hydroxyl group rich in reactivity, and any conventionally known one can be arbitrarily used. can do. For example, C1-C5 lower alkoxy group, acetoxy group, butanoxime group, chloro group and the like can be mentioned. Here, Ci (i is a natural number) represents that the number of carbon atoms is i. Furthermore, X may be a hydroxyl group. Moreover, these hydrolysable groups may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Among these, a C1-C5 lower alkoxy group is preferable because a component liberated after the reaction is neutral. In particular, a methoxy group or an ethoxy group is preferable because it is highly reactive and the solvent to be liberated is light boiling.
Furthermore, when X is an acetoxy group or a chloro group in the general formula (1), acetic acid and hydrochloric acid are liberated after the hydrolysis reaction. It is preferable to add the process to do.

In the general formula (1), Y ¹ can be arbitrarily selected from any known monovalent organic groups of so-called silane coupling agents. Among them, the organic group particularly useful as Y ¹ in the general formula (1) in the present invention is selected from the following group represented by Y ⁰ (useful organic group group). Furthermore, other organic groups may be appropriately selected for improving the affinity between the specific layer and other materials, improving adhesion, adjusting the refractive index of the specific layer, and the like.

<Useful organic group Y ⁰ >
Y ⁰ is a monovalent or higher-valent organic group derived from an aliphatic compound, alicyclic compound, aromatic compound, or aliphatic aromatic compound.
The number of carbon atoms of the organic group belonging to the group Y ⁰ is usually 1 or more, and usually 1000 or less, preferably 500 or less, more preferably 100 or less, and further preferably 50 or less.

Furthermore, at least a part of the hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with a substituent such as an atom and / or an organic functional group exemplified below. At this time, a plurality of hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with the following substituents. In this case, one or more selected from the following substituents may be substituted. It may be replaced by a combination.

Examples of substituents that can be substituted with hydrogen atoms of organic groups belonging to group Y ⁰ include atoms such as F, Cl, Br, and I; vinyl groups, methacryloxy groups, acryloxy groups, styryl groups, mercapto groups, epoxy groups, Examples thereof include organic functional groups such as an epoxycyclohexyl group, a glycidoxy group, an amino group, a cyano group, a nitro group, a sulfonic acid group, a carboxy group, a hydroxy group, an acyl group, an alkoxy group, an imino group, and a phenyl group.

In all of the above cases, among the substituents that can be substituted with the hydrogen atoms of the organic group belonging to the group Y ⁰ , at least a part of the hydrogen atoms of the organic functional group is F, It may be substituted with a halogen atom such as Cl, Br, or I.
However, among those exemplified as substituents capable of substituting for hydrogen of the organic group belonging to the group Y ⁰ , the organic functional group is an example that can be easily introduced, and various other physicochemical functions depending on the purpose of use. Organic functional groups having properties may be introduced.

In addition, the organic group belonging to the group Y ⁰ may have various atoms or atomic groups such as O, N, or S as a linking group therein.
In the general formula (1), Y ¹ can be selected from various groups depending on the purpose from the organic groups belonging to the above-mentioned useful organic group group Y ^0. It is preferable to use as a main component.

  Specific examples of the above-mentioned compound (1) include compounds in which M is silicon, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxy. Silane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, methyltrichlorosilane, γ-acinopropyltriethoxysilane, 4-amino Butyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimeth Xysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 4-aminobutyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxy Silane, 3-mercaptopropyl trimethoxysilane, vinyl trichlorosilane, vinyltris (2-methoxyethoxy) silane, etc. trifluoropropyl trimethoxysilane.

Examples of the compound (1) in which M is aluminum include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide, and the like.
Examples of the compound (1) in which M is zirconium include, for example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n-butoxide, Zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide and the like can be mentioned.

Moreover, as a compound whose M is titanium among compounds (1), for example, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium tetramethoxypropoxide , Titanium tetra n-propoxide, titanium tetraethoxide and the like.
However, the compounds specifically exemplified in these are some of commercially available coupling agents that are readily available. For more details, see, for example, “Optimum Utilization Technology for Coupling Agents” in Chapter 9 published by the Science and Technology Research Institute. It can be shown by a list of coupling agents and related products. Of course, the coupling agent that can be used in the present invention is not limited by these examples.

  In addition, the compound represented by the following general formula (2) (hereinafter appropriately referred to as “compound (2)”) and / or its oligomer may be used in the same manner as the above compound (1) and / or its oligomer. it can.

_{^{(M s + X t Y 1}} st-1) u Y 2 (2)

In the general formula (2), M, X and Y ¹ each independently represent the same as in the general formula (1). In particular, as Y ¹ , various groups can be selected according to the purpose from the organic groups belonging to the useful organic group group Y ⁰ as in the case of the general formula (1), but they are excellent in ultraviolet resistance and heat resistance. From the point of view, it is preferable to mainly use a methyl group.
Moreover, in General formula (2), s represents the valence of M and is an integer of 2-4. “S +” indicates that it is a positive integer.

Further, in the general formula (2), Y ² represents a u-valent organic group. Here, u represents an integer of 2 or more. Therefore, in the general formula (2), Y ² can be arbitrarily selected from divalent or higher ones among known organic groups of so-called silane coupling agents.
In the general formula (2), t represents an integer of 1 or more and s−1 or less. However, t ≦ s.

Examples of the compound (2) include those in which a plurality of hydrolyzable silyl groups are bonded as side chains to various organic polymers and oligomers, and those in which a hydrolyzable silyl group is bonded to a plurality of terminals of the molecule. Etc.
Specific examples of the compound (2) and product names thereof are listed below.
・ Bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical, KBE-846)
2-diethoxymethylethylsilyldimethyl-2-furanylsilane (manufactured by Shin-Etsu Chemical, LS-7740)
N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine (manufactured by Chisso, Silaace XS1003)
N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine (Momentive Performance Materials Japan GK, TSL8227)
N-glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine (Momentive Performance Materials Japan GK, TSL8228)
N, N-bis [(methyldimethoxysilyl) propyl] amine (Momentive Performance Materials Japan Limited, TSL8206)
N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine (Momentive Performance Materials Japan Limited, TSL8212)
・ N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide (Momentive Performance Materials Japan Limited, TSL8213)
N, N-bis [3- (trimethoxysilyl) propyl] amine (Momentive Performance Materials Japan GK, TSL8208)
N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (Momentive Performance Materials Japan Limited, TSL8214)
N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide (Momentive Performance Materials Japan Limited, TSL8215)
N, N ′, N ″ -tris [3- (trimethoxysilyl) propyl] isocyanurate (manufactured by Hydras Chemical, 12267-1)
・ 1,4-Bishydroxydimethylsilylbenzene (manufactured by Shin-Etsu Chemical Co., Ltd., LS-7325)

  As the raw material, compound (1), compound (2), and / or oligomers thereof can be used. That is, in the production method of the present invention, compound (1), oligomer of compound (1), compound (2), oligomer of compound (2), and oligomer of compound (1) and compound (2) are used as raw materials. Any of them may be used. In addition, when using the oligomer of a compound (1) or the oligomer of a compound (2) as a raw material, although the molecular weight of the oligomer is arbitrary as long as the specific layer based on this invention can be obtained, it is 400 or more normally.

  Here, when the compound (2) and / or oligomer thereof is used as a main raw material, the main chain structure in the system becomes an organic bond main body, which may be inferior in durability. For this reason, it is desirable to use the compound (2) in a minimum use amount mainly for imparting functions such as adhesion, refractive index adjustment, reactivity control, and inorganic particle dispersibility. When compound (1) and / or its oligomer (component derived from compound (1)) and compound (2) and / or its oligomer (component derived from compound (2)) are used at the same time, the compound ( 2) It is desirable that the amount of the derived component used is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.

  In the specific layer forming liquid and the specific layer manufacturing method of the present invention, when the oligomer of the compound (1) or the compound (2) is used as a raw material, the oligomer may be prepared in advance. You may make it prepare an oligomer in a manufacturing process. That is, a monomer such as compound (1) or compound (2) may be used as a raw material, and this may be used once as an oligomer in the production process, and the subsequent reaction may proceed from this oligomer.

  Moreover, the oligomer should just have a structure similar to what is obtained from a monomer like a compound (1) or a compound (2) as a result, and uses the commercially available thing which has such a structure. You can also. Specific examples of such oligomers include the following.

<Example of oligomer consisting only of bifunctional silicon>
Examples of the hydroxy-terminated dimethylpolysiloxane manufactured by Momentive Performance Materials Japan GK include XC96-723, XF3905, YF3057, YF3800, YF3802, YF3807, and YF3897.

Examples of the hydroxy-terminated methylphenylpolysiloxane manufactured by Momentive Performance Materials Japan GK include YF3804.
Examples of the both-end silanol polydimethylsiloxane manufactured by Gelest include DMS-S12 and DMS-S14.
An example of a double-ended silanol diphenylsiloxane-dimethylsiloxane copolymer manufactured by Gelest is PDS-1615.
An example of both-end silanol polydiphenylsiloxane manufactured by Gelest is PDS-9931.

<Examples of oligomers containing trifunctional or higher functional silicon>
Examples of silicone alkoxy oligomers (methyl / methoxy type) manufactured by Shin-Etsu Chemical include KC-89S, KR-500, X-40-9225, X-40-9246, and X-40-9250.

Examples of silicone alkoxy oligomers (phenyl / methoxy type) manufactured by Shin-Etsu Chemical include KR-217.
Examples of silicone alkoxy oligomers (methylphenyl / methoxy type) manufactured by Shin-Etsu Chemical include KR-9218, KR-213, KR-510, X-40-9227, and X-40-9247.

  Among these, an oligomer composed only of bifunctional silicon has a large effect of imparting flexibility to the specific layer of the optical member of the present invention, but mechanical strength tends to be insufficient with only bifunctional silicon. For this reason, the specific layer can obtain mechanical strength useful as a sealant by polymerizing together with a monomer composed of trifunctional or higher functional silicon or an oligomer containing trifunctional or higher functional silicon. Further, those having silanol as a reactive group do not need to be hydrolyzed in advance, and there is an advantage that it is not necessary to use a solvent such as alcohol as a compatibilizer for adding water. In addition, when using the oligomer which has an alkoxy group, the water for a hydrolysis is needed like the case where the monomer which has an alkoxy group is used as a raw material.

Furthermore, as a raw material, you may use only 1 type among these compounds (1), a compound (2), and its oligomer, However, You may mix 2 or more types by arbitrary combinations and compositions. Further, a compound (1), a compound (2) and an oligomer thereof hydrolyzed in advance (that is, X in the general formulas (1) and (2) is an OH group) may be used.
However, in the production method of the present invention, as a raw material, compound (1), compound (2), and oligomer thereof (hydrolyzed) containing silicon as M and having at least one organic group Y ¹ or organic group Y ² are used. It is necessary to use at least one kind. In addition, since it is preferable that the crosslinking in the system is mainly formed by inorganic components including a siloxane bond, when the compound (1) and the compound (2) are used together, the compound (1) is mainly used. It is preferable to become.

  In order to obtain a specific layer mainly composed of a siloxane bond, it is preferable to use the compound (1) and / or its oligomer as a main material. Furthermore, it is more preferable that the oligomer of the compound (1) and / or the oligomer of the compound (2) is composed of a bifunctional composition. In particular, the bifunctional unit of the oligomer of the compound (1) and / or the oligomer of the compound (2) is preferably used as a bifunctional oligomer.

  Furthermore, in the case of using mainly a bifunctional oligomer (hereinafter appropriately referred to as “bifunctional component oligomer”) among the oligomer of compound (1) and / or the oligomer of compound (2), the amount of these bifunctional component oligomers used Is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight, based on the total weight of the raw materials (that is, the sum of the weights of compound (1), compound (2), and oligomers thereof). That's it. The upper limit of the amount used is usually 97% by weight. This is because the use of the bifunctional component oligomer as the main ingredient is one of the factors that enable the specific layer to be easily manufactured by the manufacturing method of the present invention.

Hereinafter, advantages of using the bifunctional component oligomer as the main ingredient will be described in detail.
For example, in an optical member manufactured by a conventional sol-gel method, a hydrolysis / polycondensation product obtained by hydrolysis and polycondensation of the raw material (including those contained in a coating solution (hydrolysis solution)) is high. It had reaction activity. Therefore, if the hydrolysis / polycondensation product is not diluted with a solvent such as alcohol, polymerization in the system proceeds and cures quickly, making molding and handling difficult. For example, conventionally, when it is not diluted with a solvent, it may be cured even if the temperature is about 40 ° C to 50 ° C. Therefore, in order to ensure the handleability of the hydrolyzed / polycondensed product obtained after hydrolysis, it was essential to allow a solvent to coexist with the hydrolyzed / polycondensed product.

In addition, if the hydrolysis / polycondensate is dried / cured in the presence of a solvent in the hydrolysis / polycondensate, in addition to shrinkage due to dehydration condensation at the time of curing, shrinkage due to solvent removal (desolvent shrinkage) is taken into account. Is done. Thereby, in the conventional optical member, the internal stress of the cured product tends to be large, and cracks, peeling, and the like due to the internal stress are likely to occur.
Furthermore, if a bifunctional component monomer is frequently used as a raw material for the purpose of softening the optical member in order to relieve the internal stress, there is a possibility that the number of low boiling ring substances in the polycondensate increases. Since the low boiling ring is volatilized at the time of curing, when the number of low boiling rings increases, the weight yield decreases. In addition, the low-boiling annular body volatilizes from the cured product and may cause stress. Furthermore, the optical member containing a large amount of low-boiling annular bodies may have low heat resistance. For these reasons, it has heretofore been difficult to obtain an optical member as a high-performance elastomeric cured body.

  On the other hand, in the production method of the present invention, as a raw material, a low-boiling impurity having no reactive terminal is obtained by previously oligomerizing a bifunctional component in another system (that is, in a system not involved in the hydrolysis / polycondensation step). Is used as a raw material. Therefore, even if a large amount of bifunctional components (that is, the above-mentioned bifunctional component oligomers) is used, those low boiling impurities do not volatilize, and it is possible to improve the weight yield of the cured product and to have good performance. An elastomeric cured product can be obtained.

  Furthermore, the reaction activity of a hydrolysis and polycondensate can be suppressed by using a bifunctional component oligomer as a main raw material. This is presumably due to the steric hindrance and electronic effect of the hydrolyzed / polycondensed product and the decrease in the amount of silanol terminals due to the use of the bifunctional component oligomer. By suppressing the reaction activity, the hydrolysis / polycondensation product will not be cured without the presence of a solvent. Therefore, it is possible to make the hydrolysis / polycondensation product one-component and solvent-free. it can.

  In addition, since the reaction activity of the hydrolyzate / polycondensate has decreased, it has become possible to increase the curing start temperature higher than before. Therefore, when a solvent below the curing start temperature of the hydrolysis / polycondensate coexists in the hydrolysis / polycondensation product, the curing of the hydrolysis / polycondensation product starts when the hydrolysis / polycondensation product is dried. The solvent will volatilize before it is done. Thereby, even if it is a case where a solvent is used, it becomes possible to suppress generation | occurrence | production of the internal stress resulting from solvent removal shrinkage | contraction.

[2-2] Hydrolysis / polycondensation step In the present invention, first, the above-mentioned compound (1), compound (2), and / or oligomer thereof is subjected to a hydrolysis / polycondensation reaction (hydrolysis / polycondensation step). . This hydrolysis / polycondensation reaction can be carried out by a known method. Hereinafter, when referring to the compound (1), the compound (2), and the oligomer thereof without distinction, they are referred to as “raw material compounds”.

  The theoretical amount of water used for conducting the hydrolysis / polycondensation reaction of the raw material compound is a 1/2 molar ratio of the total amount of hydrolyzable groups in the system based on the reaction formula shown in the following formula (3). .

In addition, the said Formula (3) represents as an example the case where M of General formula (1), (2) is a silicon | silicone. “≡Si” and “Si≡” are represented by omitting three of the four bonds of the silicon atom.
In the present specification, the theoretical amount of water necessary for this hydrolysis, that is, the amount of water corresponding to a 1/2 molar ratio of the total amount of hydrolyzable groups is used as a standard (hydrolysis rate 100%). The amount of water used is expressed as a percentage of this reference amount, ie “hydrolysis rate”.

  In the production method of the present invention, the amount of water used for carrying out the hydrolysis / polycondensation reaction is usually 80% or more, preferably 100% or more, when expressed by the above-mentioned hydrolysis rate. When the hydrolysis rate is less than this range, hydrolysis and polymerization are insufficient, and thus the raw material may volatilize during curing or the strength of the cured product may be insufficient. On the other hand, when the hydrolysis rate exceeds 200%, free water always remains in the system during curing, causing deterioration of the phosphor and other contents due to moisture, or the substrate absorbing water and foaming during curing. May cause cracking and peeling. However, what is important in the hydrolysis reaction is that hydrolysis and polycondensation are performed with water of around 100% or more (for example, 80% or more). If a step of removing free water is added before coating, 200% is obtained. It is possible to apply a hydrolysis rate exceeding. In this case, if too much water is used, the amount of water to be removed and the amount of solvent to be used as a compatibilizer increase, the concentration process becomes complicated, and polycondensation proceeds so that each of the specific components constituting the optical member Since the coating performance of the layer may be deteriorated, the upper limit of the hydrolysis rate is usually 500% or less, particularly 300% or less, preferably 200% or less.

  When hydrolysis / condensation polymerization of the raw material compound, it is preferable to promote hydrolysis / condensation polymerization in the presence of a catalyst. In this case, examples of the catalyst used include organic acids such as acetic acid, propionic acid and butyric acid; inorganic acids such as nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid; and organometallic compound catalysts. Among these, when it is set as the structure layer used for the part which touches a board | substrate directly, an organometallic compound catalyst with little influence on an insulation characteristic is preferable. Here, the organometallic compound catalyst does not only refer to a catalyst composed of an organometallic compound in a narrow sense in which an organic group and a metal atom are directly bonded, but an organometallic complex, a metal alkoxide, an organic acid and a metal. The catalyst which consists of an organometallic compound in a broad sense including the salt of this.

Among the organometallic compound catalysts, an organometallic compound catalyst containing at least one element selected from zirconium, hafnium, tin, zinc and titanium is preferred, and an organometallic compound catalyst containing zirconium is more preferred.
Specific examples thereof include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxy. , Zirconium tetranormal butoxide, zirconium acylate, zirconium tributoxide, and the like.

Examples of titanium-containing organometallic compound catalysts include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, etc. Is mentioned.
Moreover, zinc triacetylacetonate is mentioned as an example of the organometallic compound catalyst containing zinc.

  Examples of organometallic compound catalysts containing tin include tetrabutyltin, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, dibutyltin laurate, Dioctyltin laurate, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbis (ethylhexylmalate) tin, di-normalbutylbis (2,4-pentanedionate) tin, Examples thereof include di-normal butyl butoxychlorotin, di-normal butyl diacetoxy tin, di-normal butyl dilaurate tin, and dimethyldineodecanoate tin.

In addition, these organometallic compound catalysts may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
By using the above preferred organometallic compound catalyst, when the raw material compound is hydrolyzed and polycondensed, it is possible to suppress the formation of by-product low-molecular cyclic siloxane and synthesize a specific layer forming liquid with a high yield. .

  Moreover, by using this organometallic compound catalyst, the specific layer and the optical member of the present invention using the specific layer can achieve high heat resistance. Although the reason is not clear, the organometallic compound not only promotes hydrolysis / polycondensation reaction of the raw material compound as a catalyst, but also temporarily at the silanol terminal of the hydrolysis / polycondensation product and its cured product. It can bind and dissociate, thereby adjusting the reactivity of the silanol-containing polysiloxane to (i) prevent oxidation of organic groups under high temperature conditions, (ii) prevent unnecessary crosslinking between polymers, (iii) It is thought to have an effect of preventing the main chain from being broken. Hereinafter, these actions (i) to (iii) will be described.

  (I) As prevention of oxidation of organic groups, for example, when a radical is generated on a methyl group by the action of heat, the transition metal of the organometallic compound catalyst has an effect of capturing the radical. On the other hand, the transition metal itself loses the ionic valence by radical scavenging, and thus acts with oxygen to prevent oxidation of the organic group. As a result, it is assumed that the deterioration of the specific layer will be suppressed.

  (Ii) As prevention of unnecessary crosslinking between polymers, for example, when a methyl group is oxidized by oxygen molecules, it becomes formaldehyde and a hydroxyl group bonded to a silicon atom is generated. When the hydroxyl groups thus formed are dehydrated and condensed, cross-linking points are formed between the polymers, and by increasing the number, the specific layer that is originally rubbery may become hard and brittle. However, it is presumed that the organometallic compound catalyst binds to a silanol group, thereby preventing the progress of crosslinking due to thermal decomposition.

  (Iii) To prevent the main chain from being broken, the organometallic compound catalyst binds to silanol, which suppresses the weight loss of the heat caused by the intramolecular attack of silanol and the formation of cyclic siloxane. It is presumed that the performance will be improved.

  A preferable blending amount of the organometallic compound catalyst is appropriately selected depending on the type of the catalyst to be used, but is usually 0.01% by weight or more, preferably 0.05% by weight based on the total weight of the raw materials to be hydrolyzed and polycondensed. % Or more, more preferably 0.1% by weight or more, and usually 5% by weight or less, preferably 2% by weight or less, particularly preferably 1% by weight or less. If the amount of the organometallic compound catalyst is too small, it may take too much time for curing, or sufficient mechanical strength and durability may not be obtained due to insufficient curing. On the other hand, if there are too many organometallic compound catalysts, the curing is too fast and it becomes difficult to control the physical properties of the specific layer which is a cured product, the catalyst cannot be dissolved and dispersed, and the transparency of the specific layer is impaired, or the catalyst itself There is a possibility that the specific layer that can be obtained by increasing the amount of organic substances brought into the product may be colored when used at high temperatures.

  These organometallic catalysts may be mixed into the raw material system at the time of hydrolysis and condensation, or may be divided and mixed. Further, a solvent may be used to dissolve the catalyst during hydrolysis and polycondensation, or the catalyst may be dissolved directly in the reaction solution. However, when used as the specific layer forming liquid, it is desirable to strictly distill off the solvent after the hydrolysis / polycondensation step in order to prevent foaming during heating and coloring due to heat.

  When the inside of the system is separated and becomes non-uniform during the hydrolysis / polycondensation reaction, a solvent may be used. As the solvent, for example, C1 to C3 lower alcohols, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, toluene, water and the like can be arbitrarily used. Those which do not exhibit properties are preferred because they do not adversely affect hydrolysis and polycondensation. The solvent may be used alone or in combination of two or more in any combination and ratio. Although the amount of solvent used can be freely selected, the solvent is often removed when it is applied to the substrate and on each layer, and therefore it is preferably set to the minimum necessary amount. In order to facilitate the removal of the solvent, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. In addition, even if it does not add a solvent from the exterior, since solvents, such as alcohol, are produced | generated by a hydrolysis reaction, even if it is heterogeneous at the beginning of reaction, it may become uniform during reaction.

When the hydrolysis / polycondensation reaction of the raw material compound is carried out at normal pressure, it is usually 15 ° C. or higher, preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and usually 140 ° C. or lower, preferably 135 ° C. or lower. More preferably, it is performed in a range of 130 ° C. or lower. It is possible to carry out at a higher temperature by maintaining the liquid phase under pressure, but it is preferable not to exceed 150 ° C.
Although the hydrolysis / polycondensation reaction time varies depending on the reaction temperature, it is usually 0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, more preferably It is carried out in the range of 15 hours or less. The reaction time is preferably adjusted appropriately while controlling the molecular weight.

  Under the above hydrolysis / polycondensation conditions, if the time is shortened or the temperature is too low, the hydrolysis / polymerization is insufficient and the raw material may volatilize during curing or the strength of the cured product may be insufficient. There is. In addition, if the time is too long or the temperature is too high, the molecular weight of the polymer increases and the amount of silanol in the system decreases, resulting in poor adhesion at the time of application or curing too early, resulting in a poor cured structure. It becomes uniform and tends to cause cracks. Based on the above tendency, it is desirable to appropriately select conditions according to desired physical property values.

  After the hydrolysis / polycondensation reaction is completed, the obtained hydrolysis / polycondensation product is stored at room temperature or lower until the time of use. When used as a shaped member, it should be used within 60 days, preferably within 30 days, more preferably within 15 days at room temperature storage after the completion of the hydrolysis and polycondensation reaction by heating. Is preferred. This period can be extended by low-temperature storage in a range that does not freeze as required. The storage period is preferably adjusted as appropriate while controlling the molecular weight.

  By the above operation, a hydrolysis / polycondensation product (polycondensation product) of the above raw material compound is obtained. This hydrolyzate / polycondensate is preferably liquid. However, even a solid hydrolysis / polycondensate can be used as long as it becomes liquid by using a solvent. The liquid hydrolyzate / polycondensate obtained in this way is a specific layer forming liquid that becomes a specific layer of the optical member of the present invention by curing in the steps described later.

[2-3] Solvent distillation When a solvent is used in the hydrolysis / polycondensation step, it is usually preferable to distill off the solvent from the hydrolysis / polycondensate before drying (solvent distillation). Process). Thereby, the specific layer formation liquid (liquid hydrolysis and polycondensation product) which does not contain a solvent can be obtained. As described above, conventionally, when the solvent is distilled off, the hydrolysis / polycondensation product is cured, making it difficult to handle the hydrolysis / polycondensation product. However, in the production method of the present invention, when the bifunctional component oligomer is used, the reactivity of the hydrolysis / polycondensation product is suppressed. The solvent can be distilled off. By distilling off the solvent before drying, cracking, peeling, disconnection, and the like due to solvent removal shrinkage can be prevented.

Usually, when the solvent is distilled off, the water used for the hydrolysis is also distilled off. Moreover, the solvent represented by XH etc. produced | generated by the hydrolysis and polycondensation reaction of the raw material compound represented by said general formula (1), (2) is also contained in the solvent distilled off. Furthermore, low molecular cyclic siloxane by-produced during the reaction is also included.
The method for distilling off the solvent is arbitrary as long as the effects of the present invention are not significantly impaired. However, it should be avoided that the solvent is distilled off at a temperature higher than the curing start temperature of the hydrolysis / polycondensate.

  When a specific range of the temperature conditions when the solvent is distilled off is given, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 150 ° C. or lower, preferably 130 ° C. or lower. More preferably, it is 120 degrees C or less. If the lower limit of this range is not reached, the solvent may be insufficiently distilled, and if the upper limit is exceeded, the hydrolysis / polycondensate may be gelled.

Further, the pressure condition when the solvent is distilled off is usually atmospheric pressure. Further, if necessary, the pressure is reduced so that the boiling point of the reaction solution when the solvent is distilled off does not reach the curing start temperature (usually 120 ° C. or higher). The lower limit of the pressure is such that the main component of the hydrolysis / polycondensate does not distill.
Generally, light boiling components can be efficiently distilled off under high temperature and high vacuum conditions. However, if the amount of light boiling components is very small, it cannot be accurately distilled off due to the shape of the equipment. There is sex. Further, when a predetermined type of catalyst is used, it may be deactivated when subjected to a high temperature reaction for a long time, and the specific layer forming liquid may be difficult to cure. Therefore, in these cases, the light boiling components may be distilled off at low temperature and normal pressure by blowing nitrogen or steam distillation, if necessary.

In any case such as distillation under reduced pressure or nitrogen blowing, it is desirable to increase the molecular weight appropriately in the previous hydrolysis / polycondensation reaction so that the main body of the hydrolysis / polycondensate does not distill. .
Optical members equipped with a specific layer produced by using a specific layer forming liquid that sufficiently removes light-boiling components such as solvents, moisture, by-product low-molecular cyclic siloxane, and dissolved air by these methods are vaporized for light-boiling components. This is preferable because it can reduce foaming during curing due to, and peeling from the substrate or each layer during high temperature use.

  However, distilling off the solvent is not an essential operation. In particular, when a solvent having a boiling point equal to or lower than the curing temperature of the hydrolysis / polycondensate is used, the solvent before the hydrolysis of the hydrolysis / polycondensation is started at the time of drying the hydrolysis / polycondensation product. Since volatilization occurs, the generation of cracks and the like due to desolvation shrinkage can be prevented without particularly performing the solvent distillation step. However, since the volume of the hydrolyzate / polycondensate may change due to the volatilization of the solvent, it is preferable to distill off the solvent from the viewpoint of precisely controlling the dimensions and shape of the optical member.

[2-4] Application The specific layer forming liquid thus obtained is applied to a desired site such as a substrate to form a coating film. This coating film becomes a specific layer by drying as described later. In addition, when performing the said solvent distillation, you may apply | coat before solvent distillation and may apply | coat after solvent distillation.

When coating, the thickness of the coating film may be set to an appropriate size according to the thickness of the specific layer to be formed. At this time, since the specific layer according to the present invention can be made thicker than a layer formed by the conventional technique, there is an advantage that the degree of freedom of dimension setting is large.
Moreover, although there is no restriction | limiting in the method used for application | coating, For example, the casting method, the spin method, the dipping method etc. can be used.

[2-5] Drying The specific layer can be obtained by drying the hydrolysis / polycondensation product obtained by the hydrolysis / polycondensation reaction described above (drying step or curing step). As described above, this hydrolyzed / polycondensed product is usually in a liquid state, but by drying it in a mold of the desired shape, a specific layer having the desired shape is formed. Is possible. Moreover, it becomes possible to form a specific layer directly in the target site | part by drying in the state which apply | coated this hydrolysis and polycondensate to the target site | part as mentioned above. In addition, although a solvent does not necessarily evaporate in a drying process, it shall call here a drying process including the phenomenon that the hydrolyzed hydrolysis-polycondensate having fluidity loses fluidity and hardens. Therefore, when there is no vaporization of the solvent, the above “drying” may be recognized as “curing”.

In the drying step, the hydrolysis / polycondensate is further polymerized to form a metalloxane bond, and the polymer is dried and cured to obtain a specific layer.
At the time of drying, the hydrolysis / polycondensate is heated to a predetermined curing temperature to be cured. The specific temperature range is arbitrary as long as the hydrolysis / polycondensate can be dried. However, since the metalloxane bond is usually formed efficiently at 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. This is done. However, when heating an optical member including a light source such as a substrate or a semiconductor light-emitting device, drying is usually performed at a temperature lower than the heat-resistant temperature of a component such as a light source such as a substrate or a semiconductor light-emitting device, preferably 200 ° C. or lower. It is preferable to do.

In addition, the time for maintaining the curing temperature (curing time) for drying the hydrolyzed / polycondensate is not generally determined depending on the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or longer, preferably 0.8. 5 hours or more, more preferably 1 hour or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.
In addition, the temperature raising conditions in the drying step are not particularly limited. That is, it may be maintained at a constant temperature during the drying process, or the temperature may be changed continuously or intermittently. In addition, the drying process may be further divided into a plurality of times. Further, in the drying process, the temperature may be changed stepwise. By changing the temperature stepwise, it is possible to obtain an advantage that foaming due to residual solvent or dissolved water vapor can be prevented. Moreover, when it hardens | cures at low temperature and it carries out additional curing at high temperature, the advantage that an internal stress is hard to generate | occur | produce in the obtained specific layer, and it is hard to raise | generate a crack and peeling can also be acquired.

  However, when the hydrolysis / polycondensation reaction described above is performed in the presence of a solvent, the solvent is not contained in the hydrolysis / polycondensate even if the solvent distillation step is not performed or the solvent distillation step is performed. Is left in the drying step, the first drying step for substantially removing the solvent at a temperature below the boiling point of the solvent and the second drying step at a temperature above the boiling point of the solvent. It is preferable to carry out the process separately from the drying step. The “solvent” mentioned here includes a solvent represented by XH or the like and a low-molecular cyclic siloxane produced by the hydrolysis / polycondensation reaction of the above-mentioned raw material compounds. Further, “drying” in the present specification refers to a step in which the hydrolysis / polycondensation product of the raw material compound loses the solvent and is further polymerized and cured to form a metalloxane bond.

  In the first drying step, the contained solvent is substantially removed at a temperature not higher than the boiling point of the solvent without actively proceeding with further polymerization of the hydrolysis / polycondensate of the raw material compound. . That is, the product obtained in this step is a product of hydrolysis / polycondensate before drying, which is concentrated into a viscous liquid or soft film by hydrogen bonding, or is hydrolyzed after removal of the solvent. The polycondensate is present in liquid form.

  However, it is usually preferable to perform the first drying step at a temperature lower than the boiling point of the solvent. When the first drying is performed at a temperature equal to or higher than the boiling point of the solvent, the resulting film is foamed by the vapor of the solvent, making it difficult to obtain a uniform film having no defects. This first drying step may be performed in a single step when the efficiency of solvent evaporation is high, such as when a thin film member is used, but when the evaporation efficiency is low, the temperature is divided into a plurality of steps. You may do it. In the case of a shape with extremely poor evaporation efficiency, it may be dried and concentrated in advance in another efficient container, and then applied in a state where the fluidity remains, and further dried. When the evaporation efficiency is poor, it is preferable to devise a method in which the whole member is uniformly dried without taking a means of concentrating only the surface of the member, such as ventilation drying with a large amount of air.

  In the second drying step, the hydrolysis / polycondensate is heated at a temperature equal to or higher than the boiling point of the solvent in a state where the solvent of the hydrolysis / polycondensation product is substantially eliminated by the first drying step, By forming a metalloxane bond, a stable cured product is obtained. If a large amount of solvent remains in this step, the volume is reduced due to evaporation of the solvent while the crosslinking reaction proceeds, so that a large internal stress is generated, causing peeling and cracking due to shrinkage. Since the metalloxane bond is usually formed efficiently at 100 ° C. or higher, the second drying step is preferably performed at 100 ° C. or higher, more preferably 120 ° C. or higher. However, when heating an optical member including a light source such as a substrate or a semiconductor light emitting device, drying is usually performed at a temperature lower than the heat resistant temperature of a component such as a light source such as a substrate or a semiconductor light emitting device, preferably 200 ° C. or lower. It is preferable to do. The curing time in the second drying step is not generally determined by the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, and usually 10 It is carried out for a period of time or less, preferably 5 hours or less, more preferably 3 hours or less.

Thus, by separating the solvent removal step (first drying step) and the curing step (second drying step) clearly, the above-described characteristics can be obtained even when the solvent distillation step is not performed. It is possible to obtain a specific layer having excellent light resistance and heat resistance without cracking or peeling.
However, curing may proceed even during the first drying step, and solvent removal may also proceed during the second drying step. However, the curing during the first drying step and the solvent removal during the second drying step are usually small enough not to affect the effects of the present invention.

  In addition, as long as the above-mentioned 1st drying process and 2nd drying process are implement | achieved substantially, the temperature rising conditions in each process are not restrict | limited in particular. That is, it may be held at a constant temperature during each drying step, or the temperature may be changed continuously or intermittently. In addition, each drying step may be further divided into a plurality of times. Furthermore, even when the temperature temporarily becomes higher than the boiling point of the solvent during the first drying step, or when there is a period during which the temperature becomes lower than the boiling point of the solvent during the second drying step, In particular, so long as the solvent removal step (first drying step) and the curing step (second drying step) as described above are achieved independently, they are included in the scope of the present invention.

  Further, when a solvent having a boiling point below the curing temperature of the hydrolysis / polycondensate, preferably less than the curing temperature is used as the solvent, the solvent present in the hydrolysis / polycondensation product has a particularly high temperature. Even if the hydrolysis / polycondensation product is heated to the curing temperature without adjustment, it will be distilled off from the hydrolysis / polycondensation product when the temperature reaches the boiling point during the drying process. . That is, in this case, in the process of raising the hydrolysis / polycondensate to the curing temperature in the drying step, the solvent is substantially removed at a temperature below the boiling point of the solvent before the hydrolysis / polycondensation product is cured. The process (1st drying process) to perform is implemented. Thereby, the hydrolysis / polycondensation product becomes a liquid hydrolysis / polycondensation product containing no solvent. After that, drying is performed at a temperature equal to or higher than the boiling point of the solvent (that is, the curing temperature), and a step of curing the hydrolysis / polycondensate (second drying step) proceeds. Therefore, when a solvent having a boiling point equal to or lower than the curing temperature is used as the solvent, the first drying step and the second drying step are performed even if the implementation is not intended. For this reason, use of a solvent having a boiling point not higher than the curing temperature of the hydrolysis / polycondensate, preferably less than the above-mentioned curing temperature, is that the hydrolysis / polycondensation product contains a solvent when performing the drying step. Even if it does, it does not have a big influence on the quality of a specific layer and the optical member provided with the said specific layer, and can be said to be preferable.

[2-6] Others After the above-described drying step, various post-treatments may be performed on the obtained specific layer as necessary. Examples of the post-treatment include surface treatment for improving adhesion, production of an antireflection film, production of a fine uneven surface for improving light extraction efficiency, and the like.

[3] Specific Layer Forming Liquid As described above, the specific layer forming liquid of the present invention is a liquid material obtained by a hydrolysis / polycondensation process and becomes a specific layer by being cured in a drying process. .

  When the specific layer forming liquid is a curable organopolysiloxane, a branched organopolysiloxane is preferable to a linear organopolysiloxane in terms of the thermal expansion coefficient of the cured product. The cured product of linear organopolysiloxane is elastomeric and has a large thermal expansion coefficient, but the thermal expansion coefficient of the cured product of branched organopolysiloxane is larger than the thermal expansion coefficient of the cured product of linear organopolysiloxane. This is because the change in optical characteristics accompanying thermal expansion is small.

Although the viscosity of the specific layer forming liquid of the present invention is not limited, at a liquid temperature of 25 ° C., it is usually 20 mPa · s or more, preferably 100 mPa · s or more, more preferably 200 mPa · s or more, and usually 1500 mPa · s or less. Preferably it is 1000 mPa * s or less, More preferably, it is 800 mPa * s or less. The viscosity can be measured with an RV viscometer (for example, an RV viscometer “RVDV-II ⁺ Pro” manufactured by Brookfield).

  Moreover, although there is no restriction | limiting in the weight average molecular weight and molecular weight distribution of the specific layer forming liquid of this invention, Usually, it is as having demonstrated in "[1-5-7] molecular weight." Furthermore, it is preferable that the low boiling point component in the specific layer forming liquid of the present invention is small, like the specific layer of the present invention described in “[1-5-8] Low boiling point component”.

[4] Other components The specific layer may contain arbitrary components without departing from the gist of the present invention. Therefore, the specific layer and the specific layer forming liquid may contain other components in addition to the hydrolysis / polycondensate described above depending on the application. For example, you may make a specific layer and a specific layer formation liquid contain a fluorescent substance, an inorganic particle, etc. as needed. Moreover, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio. In addition, you may contain these other components in layers other than the specific layer which comprises an optical member.
Hereinafter, the phosphor and the inorganic particles will be described.

[4-1] Phosphor The optical member of the present invention can contain, for example, a phosphor in a phosphor-containing layer described later. In addition, fluorescent substance may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. Further, the phosphor may be contained in two or more layers among the layers constituting the optical member of the present invention.

[4-1-1] Type of phosphor The composition of the phosphor is not particularly limited, but a metal oxide represented by Y ₂ O ₃ , Zn ₂ SiO _4, or the like that is a crystal matrix, Ca ₅ (PO ₄ ) ₃ Cl or the like phosphate and ZnS typified, SrS, sulfide represented by CaS or the like, Ce, Pr, Nd, Pm , Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb , etc. A combination of rare earth metal ions and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators is preferred.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , aluminate such as Y ₃ Al ₅ O ₁₂ , Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) halophosphate such as ₆ Cl _2, Sr ₂ P _{2 7,} it may be mentioned (La, Ce) phosphate PO _4, etc. and the like.

However, the above-mentioned crystal matrix and activator or coactivator are not particularly limited in elemental composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the examples of the phosphors in this specification, phosphors that are different only in a part of the structure are appropriately omitted. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb”. ³⁺ ”,“ La ₂ O ₂ S: Eu ”,“ Y ₂ O ₂ S: Eu ”and“ (La, Y) ₂ O ₂ S: Eu ”are changed to“ (La, Y) ₂ O ₂ S: “Eu” collectively. Omitted parts are separated by commas (,).

[4-1-1-1] Red phosphor A specific wavelength range of fluorescence emitted by a phosphor emitting red fluorescence (hereinafter referred to as “red phosphor” as appropriate) is exemplified. A peak wavelength is usually 570 nm. Above, preferably 580 nm or more, and usually 700 nm or less, preferably 680 nm or less.

Examples of such a red phosphor include europium activation represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. An alkaline earth silicon nitride-based phosphor, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu Examples thereof include europium-activated rare earth oxychalcogenide phosphors.

  Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu, Mn, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ ( SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu-activated silicate phosphor such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce _{, (Tb, Gd) 3 Al} 5 O 12: Ce -activated aluminate phosphor such as Ce, (Ca, Sr, Ba ) 2 Si 5 N 8: Eu, ( g, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride phosphor such as Eu, (Mg, Ca, Sr , Ba) AlSiN 3: Ce , etc. Ce-activated nitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, (Ba ₃ Mg) Si _{2 O 8: Eu, Mn, (} Ba, Sr, Ca, Mg) 3 (Zn, Mg) Si 2 O 8: Eu, Eu such as Mn, Mn-activated silicate phosphor, 3.5MgO · 0.5MgF ₂ GeO ₂ : Mn-activated germanate phosphor such as Mn, Eu-activated oxynitride phosphor such as Eu-activated α sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi, etc. eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Eu Bi, etc., with Bi Oxysulfide phosphor, (Gd, Y, Lu, La) VO 4: Eu, Eu Bi, etc., Bi-activated vanadate phosphor, SrY ₂ S _4: Eu, such as Ce Eu, Ce-activated sulfide Phosphor, Ca-activated sulfide phosphor such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) ) _X Si _{y Nz} : Eu, Ce activated nitride phosphor such as Eu, Ce (where x, y, z are integers of 1 or more), (Ca, Sr, Ba, Mg) ₁₀ (PO _{4 ) 6 (F, Cl, Br} , OH): Eu, Eu such as Mn, Mn-activated halophosphate phosphor, ((Y, Lu, Gd , Tb) 1-x S It is also possible to use _{x Ce y) 2 (Ca,} Mg) 1-r (Mg, Zn) 2 + r Si zq Ge q O 12 + δ Ce -activated silicate phosphor such like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Of the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn ²⁺ , SrCaAlSiN ₃ : Eu, Eu-activated α sialon, etc. Examples include Eu-activated oxynitride phosphors.

[4-1-1-2] Green phosphor A specific wavelength range of fluorescence emitted by a phosphor emitting green fluorescence (hereinafter referred to as “green phosphor” as appropriate) is exemplified. A peak wavelength is usually 490 nm. Above, preferably 500 nm or more, and usually 570 nm or less, preferably 550 nm or less.
As such a green phosphor, for example, a europium activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

In addition, as the green phosphor, Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al _{2 Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Tb-activated silicate phosphor such as Ce and Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu such as Eu Activated borate phosphor, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu activated halosilicate phosphor such as Eu, Zn ₂ SiO ₄ : Mn activated silicate phosphor such as Mn, CeMgAl ₁₁ O _{19: Tb, Y 3 Al 5} O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2 _{Tb, La 3 Ga 5 SiO 14} : Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4: Eu, Tb, and Sm, such as Eu, Tb, Sm-activated thiogallate phosphor, Ce-activated aluminate phosphor such as Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce, Ca-activated silicate phosphor such as Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, Ce-activated such as CaSc ₂ O ₄ : Ce Oxide phosphors, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu-activated oxynitride phosphors such as Eu-activated β-sialon, BaMgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu and Mn, SrAl ₂ O ₄ : Eu activated alumina such as Eu Salt phosphor, Tb activated oxysulfide phosphor such as (La, Gd, Y) ₂ O ₂ S: Tb, Ce, Tb activated phosphate phosphor such as LaPO ₄ : Ce, Tb, ZnS: Cu , Al, ZnS: sulfide phosphors such as Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba , Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb, etc., Eu such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, etc. , Mn-activated halosilicate phosphor, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphor or thiogallate phosphor such as Eu, (Ca, Sr) _{8 (Mg, Zn) (SiO 4} ) 4 Cl 2: Eu, Eu such as Mn, also possible to use Mn-activated halo-silicate phosphors such A.

  Examples of green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes, terbium complexes having hexyl salicylate as a ligand, etc. It is also possible to use organic phosphors.

[4-1-1-3] Blue phosphor A specific wavelength range of fluorescence emitted by a phosphor emitting blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate) is exemplified. A peak wavelength is usually 420 nm. Above, preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less.
As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting light in a blue region. Europium activated halo represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of phosphors and growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region. Calcium phosphate-based phosphor, composed of growing particles having an approximately cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu It is composed of alkaline earth chloroborate phosphors and fractured particles having fractured surfaces, and emits light in the blue-green region (S _{, Ca, Ba) Al 2 O} 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: activated alkaline earth with europium aluminate-based phosphor such as represented by Eu and the like.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu activation such as Eu, Mn, Sb Halophosphate phosphor, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ Eu-activated silicate phosphor such as MgSi ₂ O ₈ : Eu, Eu-activated phosphate phosphor such as Sr ₂ P ₂ O ₇ : Eu, sulfide fluorescence such as ZnS: Ag, ZnS: Ag, Al Body, Ce activated silicate phosphor such as Y ₂ SiO ₅ : Ce, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn-activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu-activated halosilicate phosphor such as Eu can be used.
In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .

[4-1-1-4] Yellow phosphor A specific wavelength range of fluorescence emitted by a phosphor emitting yellow fluorescence (hereinafter referred to as “yellow phosphor” as appropriate) is usually 530 nm or more, preferably Is preferably in the wavelength range of 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. If the emission peak wavelength of the yellow phosphor is too short, the yellow component may be reduced and color rendering may be inferior. If it is too long, the luminance of light emitted from the optical member may be reduced.

Examples of such yellow phosphors include various oxide, nitride, oxynitride, sulfide, and oxysulfide phosphors. In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element of Y, Tb, Gd, Lu, and Sm, and M represents at least one element of Al, Ga, and Sc. . representing) and ^{_{M 2 3 M 3 2 M 4}} 3 O 12: Ce ( here, M ² is a divalent metal element, M ³ is a trivalent metal element, M ⁴ is a tetravalent metal element), etc. Garnet-based phosphor having a garnet structure, AE ₂ M ⁵ O ₄ : Eu (where AE represents at least one element of Ba, Sr, Ca, Mg, Zn, and M ⁵ represents Si , Ge represents at least one element)), oxynitride phosphors in which part of oxygen of the constituent elements of these phosphors is replaced by nitrogen, AEAlSiN ₃ : Ce (where AE is an element of at least one of Ba, Sr, Ca, Mg, Zn) And a phosphor activated with Ce such as a nitride-based phosphor having a CaAlSiN ₃ structure.
Also, In addition, as the yellow _{phosphor, CaGa 2 S 4: Eu (} Ca, Sr) Ga 2 S 4: Eu, (Ca, Sr) (Ga, Al) 2 S 4: sulfide-based phosphor such as Eu It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a SiAlON structure such as Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu.

[4-1-1-5] Other Phosphors The optical member of the present invention can contain phosphors other than those described above. For example, the layer constituting the optical member of the present invention may be a fluorescent glass in which an ionic fluorescent material or an organic / inorganic fluorescent component is dissolved and dispersed uniformly and transparently.

[4-1-2] Particle Size of Phosphor The particle size of the phosphor used in the present invention is not particularly limited, but is the median particle size (D ₅₀ ), usually 0.1 μm or more, preferably 2 μm or more, and Preferably it is 5 micrometers or more. Moreover, it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 20 micrometers or less. When the median particle diameter (D ₅₀ ) of the phosphor is in the above range, light transmitted from the light source is sufficiently scattered in the phosphor-containing layer described later. In addition, since the light transmitted from the light source is sufficiently absorbed by the phosphor particles, wavelength conversion is performed with high efficiency, and light emitted from the phosphor is irradiated in all directions. Thereby, primary light from a plurality of types of phosphors can be mixed to make white, and uniform white light and illuminance can be obtained. On the other hand, when the median particle diameter (D ₅₀ ) of the phosphor is larger than the above range, the phosphor cannot sufficiently fill the space of the light emitting part, and thus the light transmitted from the light source is not sufficiently absorbed by the phosphor. there is a possibility. In addition, when the median particle diameter (D ₅₀ ) of the phosphor is smaller than the above range, the luminous efficiency of the phosphor is lowered, and the illuminance may be lowered.

The particle size distribution (QD) of the phosphor particles is preferably smaller in order to align the dispersed state of the particles in the phosphor-containing layer. However, in order to reduce the particle size, the classification yield is lowered and the cost is increased. 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more. Moreover, it is 0.4 or less normally, Preferably it is 0.3 or less, More preferably, it is 0.2 or less.
In the present invention, the median particle size (D ₅₀ ) and particle size distribution (QD) can be obtained from a weight-based particle size distribution curve. The weight-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method, and specifically, for example, can be measured as follows.

[Method for measuring weight-based particle size distribution curve]
(1) A phosphor is dispersed in a solvent such as ethylene glycol in an environment where the temperature is 25 ° C. and the humidity is 70%.
(2) Measurement is performed in a particle size range of 0.1 μm to 600 μm with a laser diffraction particle size distribution measuring device (Horiba LA-300).
(3) In this weight-based particle size distribution curve, the particle size value when the integrated value is 50% is expressed as the median particle size D ₅₀ . Further, the particle size values when the integrated values are 25% and 75% are expressed as D ₂₅ and D ₇₅ , respectively, and defined as QD = (D ₇₅ −D ₂₅ ) / (D ₇₅ + D ₂₅ ). A small QD means a narrow particle size distribution.

  Further, the shape of the phosphor particles is arbitrary as long as it does not affect the formation of the phosphor-containing layer. For example, a forming liquid for forming a phosphor-containing layer (hereinafter, referred to as “phosphor-containing layer forming liquid” as appropriate. For example, a specific layer forming liquid containing a phosphor, etc. As long as it does not affect the fluidity or the like.

[4-1-3] Phosphor surface treatment The phosphor used in the present invention is subjected to a surface treatment for the purpose of enhancing water resistance or preventing unnecessary aggregation of the phosphor in the phosphor-containing layer. It may be broken. Examples of such surface treatment include surface treatment using an organic material, an inorganic material, a glass material and the like described in JP-A-2002-223008, and coating with a metal phosphate described in JP-A-2000-96045 and the like. Examples thereof include known treatments such as treatment, coating treatment with metal oxide, and silica coating.

As specific examples of the surface treatment, for example, the following surface treatments (i) to (iii) are performed in order to coat the surface of the phosphor with the metal phosphate.
(I) A predetermined amount of a water-soluble phosphate such as potassium phosphate or sodium phosphate, and at least one of alkaline earth metals such as calcium chloride, strontium sulfate, manganese chloride, and zinc nitrate, Zn and Mn The water-soluble metal salt compound is mixed in the phosphor suspension and stirred.
(Ii) A phosphate of at least one metal among alkaline earth metals, Zn and Mn is generated in the suspension, and the generated metal phosphate is deposited on the phosphor surface.
(Iii) Remove moisture.

Further, among other examples of surface treatment, suitable examples include silica coating, a method of neutralizing water glass to precipitate SiO ₂ , a method of surface treatment of hydrolyzed alkoxysilane (for example, In view of enhancing dispersibility, a method of subjecting a hydrolyzed alkoxysilane to a surface treatment is preferable.

[4-1-4] Method of mixing phosphors In the present invention, the method of adding phosphor particles is not particularly limited. For example, when the phosphor is contained in the specific layer, it is only necessary to post-mix the phosphor into the specific layer forming liquid as long as the phosphor particles are well dispersed. That is, the specific layer forming liquid and the phosphor are mixed, a phosphor-containing layer forming liquid is prepared, and the phosphor-containing layer is prepared using this phosphor-containing layer forming liquid. In the case where the aggregation of the phosphor particles is likely to occur, the phosphor particles are mixed in advance with a reaction solution containing the raw material compound before hydrolysis (hereinafter referred to as “pre-hydrolysis solution” as appropriate), and in the presence of the phosphor particles. When the hydrolysis / polycondensation is carried out at, the surface of the particles is partially subjected to silane coupling treatment, and the dispersed state of the phosphor particles is improved.

  Although some phosphors are hydrolyzable, the specific layer of the optical member of the present invention is potentially present as a silanol body in the liquid state before application (specific layer forming liquid). Since there is almost no free water, such a phosphor can be used without being hydrolyzed. Further, if the specific layer forming liquid after hydrolysis and polycondensation is used after dehydration and dealcoholization treatment, there is an advantage that it can be easily used together with such a phosphor.

  Further, when phosphor particles or inorganic particles (described later) are dispersed in a specific layer, the particle surface can be modified with an organic ligand to improve dispersibility. Conventionally, addition type silicone resins that have been used as optical members are susceptible to curing inhibition by such organic ligands, and particles subjected to such surface treatment cannot be mixed and cured. This is because the platinum-based curing catalyst used in the addition reaction type silicone resin has a strong interaction with these organic ligands, loses the hydrosilylation ability, and causes poor curing. Such poisonous substances include organic compounds containing multiple bonds, such as organic compounds containing N, P, S, etc., ionic compounds of heavy metals such as Sn, Pb, Hg, Bi, As, acetylene groups, etc. Amines, vinyl chloride, sulfur vulcanized rubber) and the like. On the other hand, the specific layer of the optical member of the present invention is based on a condensation type curing mechanism that hardly causes curing inhibition by these poisoning substances. For this reason, the specific layer has a high degree of freedom of mixing with fluorescent particles such as phosphor particles and inorganic particles whose surface has been modified with an organic ligand, and further fluorescent components such as complex phosphors, phosphor binders and high refractive index nanoparticles It has excellent characteristics as an introduced transparent material.

[4-1-5] Phosphor Content The phosphor content in the phosphor-containing layer of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, and can be freely selected depending on the application form. The total amount of the phosphor is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 35% by weight or less, preferably 30% by weight or less, more preferably 28% by weight or less. It is.

  In general, when a white color is obtained by mixing the emission color of light transmitted from the light source and the emission color of the phosphor, a part of the emission color of the light transmitted from the light source is transmitted. The content rate is low and becomes a region near the lower limit of the above range. On the other hand, when white light is obtained by converting all the light transmitted from the light source to the phosphor emission color, a high concentration phosphor is preferable, and the phosphor content is in a region near the upper limit of the above range. If the phosphor content is higher than this range, the coating performance may be deteriorated, or the utilization efficiency of the phosphor may be lowered due to the optical interference action, and the luminance may be lowered. On the other hand, if the phosphor content is less than this range, wavelength conversion by the phosphor becomes insufficient, and the target emission color may not be obtained.

As described above for the use of white light emission, the specific phosphor content varies depending on the target color, phosphor luminous efficiency, color mixture type, phosphor specific gravity, coating film thickness, and optical member shape. Absent.
By the way, for example, when a phosphor is contained in a specific layer to constitute a phosphor-containing layer, the specific layer forming liquid has a lower viscosity than conventional optical member forming liquids such as epoxy resins and silicone resins, In addition, it has an advantage that the coating performance is sufficiently maintained even if a high concentration of phosphor and inorganic particles are dispersed. In addition, it is possible to increase the viscosity by adjusting the degree of polymerization and adding a thixo material such as aerosil as necessary, and the adjustment range of the viscosity according to the target phosphor content is large. It is possible to provide a coating solution that can flexibly cope with various types and shapes as well as various coating methods such as potting, spin coating and printing.

  In addition, the phosphor content in the phosphor-containing layer is such that if the phosphor composition can be specified, the phosphor-containing sample is pulverized and pre-fired, and after removing the carbon component, the silicon component is converted to silicic acid by hydrofluoric acid treatment. The residue is dissolved in dilute sulfuric acid to make the main component metal element into an aqueous solution, and the main component metal element is quantified by a known element analysis method such as ICP, flame analysis, fluorescent X-ray analysis, etc. The content rate can be determined. In addition, if the phosphor shape and particle size are uniform and the specific gravity is known, a simple method can be used in which the number of particles per unit area is obtained by image analysis of the cross-section of the coating and converted into the phosphor content.

  Moreover, what is necessary is just to set the content rate of the fluorescent substance in a fluorescent substance containing layer formation liquid so that the content rate of the fluorescent substance in a fluorescent substance containing layer may be settled in the said range. Therefore, when the weight of the phosphor-containing layer forming liquid does not change in the drying step, the phosphor content in the phosphor-containing layer forming liquid is the same as the phosphor content in the phosphor-containing layer. In addition, when the phosphor-containing layer forming liquid changes in weight in the drying process, such as when the phosphor-containing layer forming liquid contains a solvent or the like, the phosphor in the phosphor-containing layer forming liquid excluding the solvent or the like The phosphor content rate may be the same as the phosphor content rate in the phosphor-containing layer.

[4-2] Inorganic particles In addition, the layer constituting the optical member of the present invention has an effect of any one of the following <1> to <5> in order to improve optical characteristics and workability. For the purpose, inorganic particles may be further contained. Especially, it is preferable that the specific layers which mutually contact among each layer which comprises the optical member of this invention contain the inorganic particle. However, in this case, at least one of the two or more specific layers included in the optical member may contain inorganic particles. The inorganic particles may be contained in only one layer among the layers constituting the optical member of the present invention, or may be contained in two or more layers.

<1> By mixing inorganic particles as a light scattering material in a light scattering layer to be described later and scattering the light transmitted from the light source, the directivity angle of the light emitted from the optical member to the outside is expanded. Further, in the phosphor-containing layer, the amount of light hitting the phosphor is increased, and the wavelength conversion efficiency is improved.
<2> The generation of cracks is prevented by blending inorganic particles as a binder in the layer constituting the optical member.
<3> The viscosity of the forming liquid is increased by blending inorganic particles as a viscosity modifier in the forming liquid for constituting each layer of the optical member.
<4> The shrinkage is reduced by adding inorganic particles to the layer constituting the optical member.
<5> By mixing inorganic particles in the layer constituting the optical member, the refractive index is adjusted to improve the light extraction efficiency.

In particular, among the above cases, when inorganic particles are contained in the specific layer, an appropriate amount of inorganic particles may be mixed in the specific layer forming liquid according to the purpose in the same manner as the phosphor powder. In this case, the effect obtained depends on the type and amount of the inorganic particles to be mixed.
For example, when the inorganic particles are ultrafine silica having a particle diameter of about 10 nm (Nippon Aerosil Co., Ltd., trade name: AEROSIL # 200), the thixotropic property of the specific layer forming liquid is increased. Is big.

Further, for example, when the inorganic particles are crushed silica or true spherical silica having a particle size of about several μm, there is almost no increase in thixotropic properties, and the function as an aggregate of a specific layer is the center. The effect <4> is great.
Further, for example, when inorganic particles having a particle size of about 1 μm different from that of the compound (dried hydrolysis / polycondensate) used in the specific layer are used, light scattering at the interface between the compound and the inorganic particles is used. Therefore, the effect <1> is great.

  Further, for example, particles having a refractive index larger than that of the compound used in the specific layer and having a median particle size of usually 1 nm or more, preferably 3 nm or more, and usually 10 nm or less, preferably 5 nm or less, specifically, an emission wavelength or less. When inorganic particles having a diameter are used, the refractive index can be improved while maintaining the transparency of the specific layer, so the effect <5> is great.

  Accordingly, the type of inorganic particles to be mixed may be selected according to the purpose. Moreover, the kind may be single and may combine multiple types. Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.

[4-2-1] Types of inorganic particles The types of inorganic particles used include inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, and yttrium oxide. Although diamond particle | grains are illustrated, according to the objective, another substance can also be selected and it is not limited to these.

  The form of the inorganic particles may be any form such as powder, slurry, etc. depending on the purpose, but if it is necessary to maintain transparency, the refractive index of other materials contained in the layer containing the inorganic particles is set. It is preferable to add them to the liquid for forming the layer as an aqueous or solvent-based transparent sol.

[4-2-2] Median particle size of inorganic particles The median particle size of these inorganic particles (primary particles) is not particularly limited, but is usually about 1/10 or less of the phosphor particles. Specifically, those having the following median particle diameter are used according to the purpose. For example, if inorganic particles are used as the light scattering material, the median particle size is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 50 μm or less, preferably 20 μm or less. For example, if inorganic particles are used as the aggregate, the median particle diameter is preferably 1 μm to 10 μm. Further, for example, if inorganic particles are used as a thickener (thixotropic agent), the center particle is preferably 10 to 100 nm. For example, if inorganic particles are used as the refractive index adjuster, the median particle size is preferably 1 to 10 nm. In particular, in the optical member of the present invention, among the specific layers in contact with each other, at least one layer contains inorganic particles having a median particle size of 0.05 to 50 μm, and the layer and / or at least one other layer has a median particle. It is preferable to contain inorganic particles having a diameter of 1 to 10 nm.

  Accordingly, optically, inorganic particles having a median particle diameter of 1 to 10 nm have an advantage that various functions such as refractive index adjustment can be imparted without impairing the transmittance of the specific layer. In addition, inorganic particles having a median particle diameter of 0.05 to 50 μm can impart functions such as scattering and fluorescence as described above. For example, when the first layer contains functional inorganic particles having a median particle size of 0.05 to 50 μm and the second layer contains only inorganic particles having a median particle size of 1 to 10 nm among the two adjacent layers The second layer having a specific refractive index and being transparent serves as a light guide layer, and the first layer is a layer that emits surface light by scattering or fluorescence. In addition, for example, both the first layer and the second layer can also contain inorganic particles having a median particle diameter of 1 to 10 nm. By setting different contents for each layer, the first layer and the second layer It is possible to make an optical design according to the light guide distance, film thickness, scattering efficiency, etc. by arbitrarily adjusting the refractive index.

[4-2-3] Method of mixing inorganic particles In the present invention, the method of mixing inorganic particles is not particularly limited. However, when mixing inorganic particles in the forming liquid, it is usually recommended to mix while defoaming using a planetary stirring mixer or the like, similarly to the phosphor. For example, when mixing small particles that easily aggregate such as Aerosil, after mixing the particles, if necessary, break up the aggregated particles using a bead mill or three rolls, and then mix large particles such as phosphor You may mix an ingredient.

[4-2-4] Content of Inorganic Particles The content of inorganic particles in each layer of the optical member of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but can be freely selected depending on the application form. For example, when using inorganic particles as a light scattering agent, the content is preferably 0.01 to 10% by weight. For example, when using inorganic particles as an aggregate, the content is preferably 1 to 50% by weight. For example, when using inorganic particles as a thickener (thixotropic agent), the content is preferably 0.1 to 20% by weight. Further, for example, when inorganic particles are used as the refractive index adjuster, the content is preferably 10 to 80% by weight. If the amount of inorganic particles is too small, the desired effect may not be obtained. If the amount is too large, various properties such as adhesion, transparency and hardness of the cured product may be adversely affected.

  As described above, when inorganic particles are included in the specific layer, the specific layer forming liquid contains inorganic particles. The specific layer forming liquid is a conventional optical member forming liquid such as an epoxy resin or a silicone resin. Compared to the above, it has a low viscosity, is well-familiar with phosphors and inorganic particles, and has an advantage that the coating performance can be sufficiently maintained even when high concentration inorganic particles are dispersed. In addition, it is possible to increase the viscosity by adjusting the degree of polymerization and adding a thixo material such as aerosil as necessary, and the adjustment range of the viscosity according to the target inorganic particle content is large. It is possible to provide a coating solution that can flexibly correspond to various coating methods such as potting, spin coating and printing.

In addition, the content rate of the inorganic particles in each layer of the optical member can be measured in the same manner as the phosphor content described above.
Moreover, what is necessary is just to set the content rate of the inorganic particle in the formation liquid for forming each layer so that the content rate of the inorganic particle in each layer may be settled in the said range. Therefore, when the forming liquid does not change in weight in the drying step, the content of inorganic particles in the forming liquid is the same as the content of inorganic particles in each layer of the optical member. In addition, when the forming liquid changes in weight in the drying step, such as when the forming liquid contains a solvent or the like, the content of inorganic particles in the forming liquid excluding the solvent or the like is the inorganic particle in each layer of the optical member. What is necessary is just to make it the same with the content rate.

[5] Layer Configuration of Optical Member The first and second optical members of the present invention are characterized in that two or more layers having different refractive indexes are laminated.
The third and fourth optical members of the present invention are characterized in that two or more layers having different haze values are laminated.
Hereinafter, the layer structure of the optical member of the present invention will be described.

[5-1] Refractive Index The first and second optical members of the present invention are characterized in that two or more layers having different refractive indexes are laminated. When the optical member of the present invention is used as an optical waveguide or a light guide plate, a high refractive index layer provides a core layer for transmitting light, and a low refractive index layer provides a light confining clad by providing a difference in refractive index between adjacent layers. Each layer is formed.

  The refractive index of the high refractive index layer of the first and second optical members of the present invention is usually 1.45 or more, preferably 1.5 or more, more preferably 1.6 or more. Although the upper limit is not particularly limited, for example, when a semiconductor light-emitting device is used as a light source, the refractive index of a general semiconductor light-emitting device is about 2.5, and is usually 2.5 or less, so that the refractive index can be easily adjusted. From the viewpoint of, it is preferably 2.0 or less. If the refractive index of the high refractive index layer is too small, the light extraction efficiency may not be improved. On the other hand, even when the refractive index of the high refractive index layer is larger than the refractive index of the member constituting the light source, the light extraction efficiency is not improved.

  Further, the refractive index of the low refractive index layer of the first and second optical members of the present invention is usually less than 1.45, preferably 1.43 or less, more preferably 1.42 or less. The lower limit is usually 1.4 or more, preferably 1.41 or more.

  The difference in refractive index between the high refractive index layer and the low refractive index layer is usually 0.03 to 0.2. By appropriately adjusting this difference, the transmission distance of light in the high refractive index layer (waveguide) (Distance) can be adjusted. In other words, when the refractive index difference is increased, the low refractive index layer (cladding layer) efficiently confines the light of the high refractive index layer (core layer), so there is less leakage light to the low refractive index layer, and the light transmission distance is reduced. Can be long. On the other hand, if the refractive index difference is set to be as small as 0.05 or less, for example, leakage light from the high refractive index layer to the low refractive index layer increases, so that the light transmission distance becomes short.

(Refractive index measurement method)
The refractive index can be measured by using a known method such as a immersion method (solid object), a Pluffich refractometer, an Abbe refractometer, a prism coupler method, an interference method, and a minimum deflection angle method. The refractive index measurement wavelength in the present invention can be selected from sodium D line (589 nm), which is used for general purposes when an instrument such as an Abbe refractometer is used.

[5-2] Haze Value The third and fourth optical members of the present invention are characterized in that two or more layers having different haze values are laminated. When a light scattering layer and / or a phosphor-containing layer is provided on the optical member of the present invention, the haze value of the light scattering layer and / or the phosphor-containing layer may be increased.

  The haze value of the light scattering layer and / or the phosphor-containing layer of the third and fourth optical members of the present invention is usually 50 or more, preferably 70 or more, more preferably 80 or more. If the haze value of the light scattering layer and / or the phosphor-containing layer is too small, the light scattering effect, that is, the effect that light is emitted to the outside of the optical member of the present invention may not be improved. Therefore, it is preferable that the haze value of at least one of the specific layers in contact with each other falls within the range of the light scattering layer and / or the phosphor-containing layer. The haze value is a numerical value of the so-called cloudiness (cloudiness value) of the transparent member, and is a value measured based on JIS-K-7136.

[5-3] Role of Each Layer As described above, the optical member of the present invention adjusts the refractive index and / or haze value of each constituent layer, thereby reducing the low refractive index layer, the high refractive index layer, and the light scattering. A layer and a phosphor-containing layer can be provided. Hereinafter, each layer will be described. In addition, the specific installation method of each layer is demonstrated by each embodiment in [6] chapter.

[5-3-1] Low Refractive Index Layer When the optical member of the present invention is used as an optical waveguide or a light guide plate as described above, a low refractive index layer is usually provided as a cladding layer for confining light. A layer other than the specific layer may be a low refractive index layer, but the low refractive index layer is preferably composed of a specific layer made of a compound having the characteristics described in the above-mentioned section [1]. Therefore, in the optical member of the present invention, it is preferable that at least one of the specific layers in contact with each other is a low refractive index layer. The refractive index of the low refractive index layer is as described above. Further, the low refractive index layer may be provided with only one layer or two or more layers.

[5-3-2] High Refractive Index Layer When the optical member of the present invention is used as an optical waveguide or a light guide plate as described above, a high refractive index layer is usually provided as a core layer for transmitting light. A layer other than the specific layer may be a high refractive index layer, but the high refractive index layer is preferably composed of a specific layer made of a compound having the characteristics described in the above-mentioned section [1]. Therefore, in the optical member of the present invention, it is preferable that at least one of the specific layers in contact with each other is a high refractive index layer.

  Further, in order to make the high refractive index layer have a higher refractive index than the low refractive index layer, for example, a phenyl group is introduced into the compound, or as described in Chapter [4-2], the refractive index adjusting agent. It is preferable to contain inorganic particles having a median particle diameter of 1 to 10 nm. The refractive index of the high refractive index layer is as described above. Further, the high refractive index layer may be provided with only one layer or two or more layers.

  Furthermore, it is more preferable that the low refractive index layer and the high refractive index layer are both constituted by specific layers. Therefore, in the optical member of the present invention, the refractive index of at least one of the specific layers in contact with each other is within the range of the high refractive index layer, and the refractive index of at least one other layer is the low refractive index layer. It is more preferable that it falls within the range.

[5-3-3] Light Scattering Layer The optical member of the present invention can be provided with a light scattering layer that radiates light transmitted from a light source to the outside. The light scattering layer functions to widen the directivity angle of light emitted from the optical member to the outside. A layer other than the specific layer may be a light scattering layer, but the light scattering layer is preferably composed of a specific layer made of a compound having the characteristics described in the above-mentioned section [1]. Further, as described in section [4-2], the light scattering layer has a median particle size of usually 0.05 μm or more, preferably 0.1 μm or more, and usually 50 μm or less, preferably as a light scattering material. It is preferable to contain inorganic particles of 20 μm or less. In addition, a light-scattering layer may provide only one layer and may provide two or more layers.

  Further, guided light can be taken out by utilizing the surface roughness of the substrate. This is because, by providing a light scattering layer on the rough surface, the guided light is scattered by the rough surface, and the component that makes the light perpendicular to the extraction surface increases, so that the light emerges on the surface. It is what I did. The rough surface can be formed on the substrate and / or on each layer. The rough surface may be formed on either the upper surface (surface close to the light extraction surface) or the lower surface (surface far from the light extraction surface) of each layer. The roughness of the rough surface is not particularly limited as long as it has the property of scattering light, but the height difference is usually 0.2 μm or more, preferably 0.5 μm or more, and usually 50 μm or less, preferably 30 μm or less.

The method of creating a rough surface on the substrate is not limited, but for example, precision machining, blasting, powder coating, application of a coating solution containing diffusing particles, particle pasting, chemical etching, light irradiation, inkjet printing, photosensitive curing ( Softening) exposure / development to resin, heating / development to thermosetting resin, and the like.
Further, as a method of roughening the surface of each layer to be laminated, for example, chemical treatment using hydrofluoric acid or alkali, blast treatment, powder coating, application of a coating solution containing diffusing particles, particle pasting, light irradiation, inkjet There is printing. In addition, for example, a method in which sedimentation or floating light diffusing particles are contained in a layer to be configured, and particles are settled or suspended after coating so that more diffusing particles exist at the interface of each layer. It can be preferably used similarly to the method of forming the surface.

[5-3-4] Phosphor-containing layer The optical member of the present invention can be provided with a phosphor-containing layer in order to convert the wavelength of light transmitted from the light source into a desired wavelength. The phosphor-containing layer refers to a layer containing a phosphor among the layers constituting the optical member. At this time, layers other than the specific layer may be a phosphor-containing layer, but the phosphor-containing layer is preferably composed of a specific layer made of a compound having the characteristics described in the above-mentioned section [1]. . In this case, among the layers constituting the optical member of the present invention, it is preferable that specific layers in contact with each other contain a phosphor to constitute a phosphor-containing layer. However, in this case, at least one of the two or more specific layers provided in the optical member may contain the phosphor.
The phosphor-containing layer is formed by containing the phosphor described in [4-1] in the layer. The phosphor-containing layer may contain inorganic particles having a median particle size of 0.1 to 10 μm as a light scattering material in order to increase the amount of light hitting the phosphor and improve the wavelength conversion efficiency. In addition, a fluorescent substance content layer may provide only one layer and may provide two or more layers.

[5-4] Shape and Size of Optical Member The shape and size of the optical member of the present invention are not limited and are arbitrary. For example, when used as an optical waveguide or light guide plate of an optical member, the shape and size of the optical member of the present invention are determined according to the shape and size of the substrate of the optical waveguide or light guide plate. Further, when formed on the surface of the substrate, it is usually formed in a film shape, and its dimensions are arbitrarily set according to the application. Further, as described above, a plurality of films having different refractive indices and haze values are laminated as the forming film (film for forming the optical member), and the dimensions of each layer are arbitrarily set according to the application.

  However, when the optical member of the present invention is formed in a film shape, one advantage is that the specific layer can be formed in a thick film. In the conventional optical member, when the layer constituting the optical member is thickened, cracks and the like are generated due to internal stress and the like, and it is difficult to thicken the film. A thick film can be stably formed. Specifically, when the optical member of the present invention is used as a light guide plate, the thickness of each specific layer is usually 10 μm or more, preferably 30 μm or more, usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less. It is. Here, when the thickness of the film is not constant, the thickness of the film refers to the thickness of the maximum thickness portion of the film. In this case, the total thickness of all layers excluding the light guide plate substrate is usually 60 μm or more, preferably 80 μm or more, and usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less.

[6] Structure of optical member Hereinafter, as an example of the optical member of the present invention, a light guide plate using a semiconductor light-emitting device as a light source will be described as an example, and will be described using an embodiment. However, these embodiments are merely used for convenience of explanation, and the optical waveguide, the light guide plate, and other examples to which the optical member of the present invention is applied are not limited to these embodiments.

[6-1] First Embodiment As shown in FIG. 1, the light guide plate 8 of the first embodiment includes a semiconductor light emitting element 2 made of an LED chip on a substrate 1 and, optionally, a semiconductor light emitting element. The semiconductor light-emitting device 4 which consists of the sealing material 3 arrange | positioned so that 2 may be coat | covered is provided as a light source.

  On the surface of the substrate 1, a low refractive index layer 5 is coated as a specific layer that is a part of the light guide plate 8. The low refractive index layer 5 is provided with a cylindrical or mortar-shaped hole 5H so as not to cover the portion of the semiconductor light emitting device 4.

  On the upper surface of the low refractive index layer 5, a high refractive index layer 6 is provided as a specific layer in contact with the low refractive index layer 5. In the present embodiment, the high refractive index layer 6 is also formed around the semiconductor light emitting device 4 in the hole 5H, so that light emitted from the semiconductor light emitting device 4 is directly incident on the high refractive index layer 6. It has become. Thereby, the high refractive index layer 6 ensures the function of transmitting light emitted from the light source (semiconductor light emitting device 4 in FIG. 1) as the core portion of the optical waveguide.

On the upper surface of the high refractive index layer 6, a low refractive index layer 5 ′ may be further provided as a specific layer in contact with the high refractive index layer 6. Even in the case where the low refractive index layer 5 ′ is not provided, the air layer can serve as a cladding portion.
A light scattering layer and / or a phosphor-containing layer 7 can be appropriately provided on the contact surface (for example, the upper surface) of the high refractive index layer 6. The light scattering layer ensures the function of emitting the light emitted from the light source transmitted by the high refractive index layer 6 to the outside. The phosphor-containing layer exhibits a wavelength conversion function of emitting light of a desired wavelength when excited by light from the light source transmitted by the high refractive index layer 6. In the light guide plate 8 of the present embodiment, light is mainly emitted from the light scattering layer and / or the phosphor-containing layer 7, so that the light scattering layer and / or the phosphor-containing layer 7 is formed. The position is preferably set in consideration of design.
In the present embodiment, the light scattering layer and / or the phosphor-containing layer 7 is formed in a predetermined portion on the upper surface of the high refractive index layer 6, and the low refractive index layer is formed on the other portion on the upper surface of the high refractive index layer 6. Assume that 5 ′ is formed.

Although there is no restriction | limiting in particular in the semiconductor light-emitting device 2, Although what emits the light which has a peak wavelength in the range of 350 nm-500 nm is preferable, a light emitting diode (LED) or a laser diode (LD) etc. are mentioned as a specific example. Can do. Of these, GaN LEDs and LDs using GaN compound semiconductors are preferred. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. GaN-based LEDs and LDs preferably have an Al _x Ga _Y N light emitting layer, a GaN light emitting layer, or an In _x Ga _Y N light emitting layer. Among GaN-based LEDs, those having an In _X Ga _Y N light-emitting layer are particularly preferable because the emission intensity is very strong, and in GaN-based LDs, the multiple quantum of the In _X Ga _Y N layer and the GaN layer is preferred. A well structure is particularly preferable because the emission intensity is very strong.

In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is composed of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a heterostructure sandwiched by Ga _Y N layers or the like have high luminous efficiency, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.

The sealing material 3 exhibits functions such as a highly durable sealant, a light extraction film, and various function-added films of the semiconductor light emitting element 2. Although the sealing material 3 may be used independently, an arbitrary additive can be contained as long as the effect of the present invention is not significantly impaired except for the phosphor and the phosphor component. Moreover, since the high refractive index layer 6 can also serve as a sealing material, the sealing material 3 may not be provided.
As the sealing material 3 to be used, the same compound as the high refractive index layer 6 of the optical member of the present invention is preferably used from the viewpoint of adhesion and the like. Moreover, as the sealing material 3, other materials can also be used. Usually, a resin (hereinafter referred to as “sealing resin” as appropriate) is used as the sealing material 3. As such a sealing resin, a thermoplastic resin, a thermosetting resin, a photocurable resin, etc. are mentioned normally. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins. Further, an inorganic material such as a siloxane bond formed by solidifying a solution obtained by hydrolyzing a solution containing an inorganic material such as a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof. An inorganic material can be used. In addition, the material of the sealing material 3 such as a sealing resin may be used alone, or two or more kinds may be used in any combination and ratio.

  The encapsulating material 3 may contain a phosphor, whereby the wavelength of the light source can be converted into light having a desired wavelength and then transmitted through the high refractive index layer. Although the usage-amount of fluorescent substance is not specifically limited, 0.01 weight part or more normally with respect to 100 weight part of sealing materials, Preferably it is 0.1 weight part or more, More preferably, it is 1 weight part or more, Moreover, it is 100 weight part or less normally, Preferably it is 80 weight part or less, More preferably, it is 60 weight part or less.

  Moreover, the sealing material 3 can also contain components other than phosphors and inorganic particles. For example, color correction dyes, antioxidants, processing / oxidation and heat stabilizers such as phosphorus-based processing stabilizers, light-resistant stabilizers such as ultraviolet absorbers, and silane coupling agents can be included. In addition, these components may be used by 1 type and may use 2 or more types together by arbitrary combinations and ratios.

  The semiconductor light emitting device 4 may be installed on the substrate 1 before coating, or may be installed on the substrate 1 after coating by removing the masking after coating and coating the installation portion. When the low refractive index layer 5, the high refractive index layer 6, and the scattering layer and / or the phosphor-containing layer 7 are formed into a thin film, a specific layer forming solution diluted with a solvent such as toluene or heptane is applied. And may be formed.

  Since the light guide plate 8 of the present embodiment is configured as described above, the light from the light source transmitted by the high refractive index layer 6 is transmitted through the light scattering layer and / or the phosphor-containing layer 7, and the optical member. Radiated to the outside of the (light guide plate 8). Therefore, when the sealing material 3 does not contain a phosphor, and when the optical member (light guide plate 8) does not contain the phosphor-containing layer 7, the light is emitted from the light source (semiconductor light emitting element 2 in FIG. 1). It is emitted to the outside in the same emission color.

The phosphor-containing layer 7 exhibits a wavelength conversion function of emitting light of a desired wavelength when excited by the light from the light source transmitted by the high refractive index layer 6 as described above. Therefore, the phosphor-containing layer 7 emits light obtained by wavelength-converting light emitted from the semiconductor light emitting element 2. At this time, the phosphor-containing layer 7 only needs to contain at least a fluorescent material that is excited by light from the light source and emits light of a desired wavelength. Examples of such fluorescent materials include the various phosphors exemplified above. As a luminescent color of the phosphor-containing layer 7, not only the three primary colors of red (R), green (G), and blue (B) but also white such as a fluorescent lamp and yellow such as a light bulb are possible. In short, the phosphor-containing layer 7 has a wavelength conversion function for emitting light having a desired wavelength different from the excitation light.
In the present embodiment, the light transmitted by the high refractive index layer 6 is also emitted from the portion where the high refractive index layer 6 on the side surface is exposed.

  Thus, the optical member (light guide plate 8) of the present embodiment has a specific structure in which the low refractive index layer 5, the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 are in contact with each other using a specific compound. Since it is formed as a layer, the optical durability (light resistance) and thermal durability (heat resistance) of the optical member (light guide plate 8) can be improved. Further, between the substrate 1 and the low refractive index layer 5, between the low refractive index layer 5 and the high refractive index layer 6, and / or the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7. Cracks and peeling are unlikely to occur between Further, since all the layers 5, 6, and 7 are formed as the above-described specific layers, there is an advantage that each of the layers can be thickened.

  Further, the angle 9 formed by the side surface of the optical member (light guide plate 8) and the laminated surface may be vertical, but the light extraction effect (particularly, the light extraction effect from the side surface portion in the present embodiment) is achieved. From the viewpoint of improvement, it is usually at least 30 °, preferably at least 35 °, more preferably at least 40 °, usually at most 80 °, preferably at most 70 °, more preferably at most 60 °. The angle formed between the side surface and the laminated surface of the optical member (light guide plate 8) is an optical member (see FIG. 1) viewed from a direction perpendicular to the laminated surface of the optical member (light guide plate 8). The inner angle formed by the side surface and the laminated surface of the light guide plate 8) is shown.

[6-2] Other Embodiments When the optical member of the present invention is applied to an optical waveguide, a light guide plate, or the like, it is preferable to make appropriate modifications according to the location to which the present invention is applied. For example, a desired number of light sources can be appropriately provided at desired positions on the substrate surface. A desired number of light scattering layers and phosphor-containing layers can be appropriately provided at desired positions of the optical member.

  Other embodiments are shown in FIGS. However, the optical member of the present invention is not limited to the embodiments exemplified below, and can be implemented with arbitrary modifications without departing from the gist of the present invention. In the following embodiments, the same parts as those described in the first embodiment are denoted by the same reference numerals as those in the first embodiment.

  In the light guide plate 8 of the second embodiment, as shown in FIG. 2, the entire uppermost layer is a light scattering layer and / or a phosphor-containing layer 7. Thus, the light can be extracted from the entire surface of the light guide plate. Further, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the above points. Therefore, the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layer 5, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 which are specific layers in contact with each other. Therefore, similar to the first embodiment, it is possible to obtain advantages such as being able to increase the thickness, suppressing cracks and peeling, and being excellent in heat resistance and light resistance.

As shown in FIG. 3, the light guide plate 8 of the third embodiment does not include the low refractive index layer 5 ′ and the light scattering layer and / or the phosphor-containing layer 7 as the uppermost layer. That is, the entire upper surface of the photorefractive index layer 6 is configured to be exposed to the gas phase. In this case, the light transmission effect is secured by the gas phase serving as the upper cladding layer. Further, as described above in [5-1], by adjusting the refractive index difference between the low refractive index layer 5 and the high refractive index layer 6, the optical waveguide distance can be controlled to achieve a desired effect. .
In the case of reducing the refractive index difference between the low refractive index layer 5 and the high refractive index layer 6, in order to achieve a desired effect using light entering the low refractive index layer 5, a light scattering layer and / or Alternatively, the phosphor-containing layer 7 can be provided on a part of the low refractive index layer 5 (FIG. 3).

  Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the above points. Therefore, the light guide plate 8 of the present embodiment also includes the low refractive index layer 5, the high refractive index layer 6, and the light scattering layer and / or the fluorescence formed on a part of the low refractive index layer 5, which are specific layers in contact with each other. Since the body-containing layer 7 is configured to be laminated, it is possible to increase the film thickness, to suppress cracks and peeling, heat resistance, and light resistance, as in the first embodiment. Advantages such as superiority can be obtained.

The light guide plate 8 of the fourth embodiment is a light scattering layer 7 by mixing a very small amount of inorganic particles as a light scattering agent in a portion corresponding to the high refractive index layer 6 of FIG. 4).
Furthermore, the light guide plate 8 according to the present embodiment has the above-described configuration and the third configuration except that the light scattering layer and / or the phosphor-containing layer 7 is not provided in part of the low refractive index layer 5 The configuration is the same as in the embodiment. Therefore, since the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layer 5 and the light scattering layer 7 which are specific layers in contact with each other, as in the third embodiment, the thick film It is possible to obtain advantages such as being capable of reducing the thickness, suppressing cracks and peeling, and being excellent in heat resistance and light resistance.

  In the light guide plate 8 of the fifth embodiment, as shown in FIG. 5, a part of the high refractive index layer 6 (high refractive index portion 6 a) that is an optical transmission portion is formed of the low refractive index layers 5, 5 ′, It penetrates the light scattering layer and / or the phosphor-containing layer 7. The high refractive index portion 6a is a boundary portion that penetrates at least two specific layers in contact with each other. In the present embodiment, since the boundary portion is formed as the high refractive index portion 6a capable of transmitting light, the light transmission portion can be extended in the direction perpendicular to the substrate surface across each layer.

  The high refractive index portion 6a may use a material different from the high refractive index layer 6 in the optical member of the present invention as a so-called “boundary portion A”. In the present embodiment, the boundary A is not particularly limited as long as it is a material that can transmit light from a light source, and an arbitrary one can be used. For example, an inorganic or organic material having the same refractive index as that of the high refractive index layer 6 can be used. Among them, the boundary A is preferably an epoxy resin, a urethane resin, a polyimide resin, an acrylic resin, or the like from the viewpoints of low moisture permeability, light blocking characteristics, and adhesion to the substrate 1. In view of adhesion to the high refractive index layer 6, the low refractive index layers 5, 5 ′, the light scattering layer and / or the phosphor-containing layer 7, an epoxy resin is particularly preferable. The use of an epoxy resin as the boundary portion A is a particularly preferable combination because the high refractive index layer 6 that is a specific layer is particularly excellent in adhesion to the epoxy resin, hardly changes in quality, and has no effect inhibition.

  There is no restriction | limiting in the preparation methods of such a high refractive index part 6a. For example, when the high refractive index portion 6a is provided on the substrate 1, before the low refractive index layers 5 and 5 ′, the high refractive index layer 6 and the light scattering layer and / or the phosphor-containing layer 7 are laminated by coating or the like. After forming the high refractive index portion 6a, the low refractive index layers 5 and 5 ′, the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 may be laminated. At this time, the method used to form the high refractive index portion 6a is not limited, and can be formed by, for example, a dispenser, screen printing, a resist method, or the like. Further, for example, a portion (hereinafter referred to as “installation portion”) where the high refractive index portion 6a on the substrate 1 is to be formed is masked, and then the low refractive index layers 5 and 5 ′, the high refractive index layer 6 and the light scattering. The layer and / or the phosphor-containing layer 7 may be laminated, and then the masking may be removed to form the high refractive index portion 6a in the installation portion. When the high refractive index portion 6a is provided on a layer other than the substrate 1, the layer is laminated on the substrate 1, and then the high refractive index portion 6a and the low refractive index portion 6a are formed on the layer according to the method described above. The necessary layers of the refractive index layers 5 and 5 ′, the high refractive index layer 6 and the light scattering layer and / or the phosphor-containing layer 7 may be formed.

  Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the above points. Therefore, the low-refractive index layers 5 and 5 ′, the high-refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other are also laminated on the light guide plate 8 of the present embodiment. Therefore, similar to the first embodiment, it is possible to increase the thickness, to suppress cracks and peeling, and to obtain advantages such as excellent heat resistance and light resistance. Can be done. In addition, if the high refractive index portion 6a is formed of the same compound as the specific layer, the high refractive index portion 6a can also be made thick, and cracks and peeling can be suppressed. Advantages such as excellent heat resistance and light resistance can be obtained.

  In the light guide plate 8 of the sixth embodiment, as shown in FIG. 6, a part of the low refractive index layer 5 (low refractive index portion 5 a) that is a light blocking portion is a high refractive index layer 6 or a light scattering layer. And / or penetrates through the phosphor-containing layer 7. The low refractive index portion 5a functions as a boundary portion. In this embodiment, since the boundary portion is formed as the low refractive index portion 5a capable of blocking light, the light blocking portion can be extended in the direction perpendicular to the substrate surface across each layer.

  The low refractive index portion 5a may use a material different from the low refractive index layer 5 in the optical member of the present invention as a so-called “boundary portion B”. In the case of this embodiment, as this boundary part B, if it is the material which can interrupt | block the light transmitted from a light source, there will be no limitation in particular and arbitrary things can be used. For example, an inorganic or organic material having a refractive index lower than that of the high refractive index layer 6 can be used. Among these, the boundary B is preferably an epoxy resin, a urethane resin, a polyimide resin, an acrylic resin, or the like from the viewpoints of low moisture permeability, light blocking characteristics, and adhesion to the substrate 1. From the viewpoint of adhesion to the high refractive index layer 6, low refractive index layers 5, 5 ′, light scattering layer and / or phosphor-containing layer 7 of the present invention, an epoxy resin is particularly preferable. The use of an epoxy resin as the boundary B is a particularly preferable combination because the high refractive index layer 6 as a specific layer is particularly excellent in adhesion with the epoxy resin, hardly changes in quality, and does not inhibit the effect.

  There is no restriction | limiting in the preparation methods of such a low refractive index part 5a. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment.

  Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the above points. Therefore, the low-refractive index layers 5 and 5 ′, the high-refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other are also laminated on the light guide plate 8 of the present embodiment. Therefore, similar to the first embodiment, it is possible to increase the thickness, to suppress cracks and peeling, and to obtain advantages such as excellent heat resistance and light resistance. Can be done. Further, if the low refractive index portion 5a is formed of the same compound as the specific layer, the low refractive index portion 5a can also be made thick, and cracks and peeling can be suppressed. Advantages such as excellent heat resistance and light resistance can be obtained.

As shown in FIG. 7, the light guide plate 8 of the seventh embodiment is obtained by installing a light scattering layer and / or a phosphor-containing layer 7 in a desired location in the high refractive index layer 6.
There is no restriction | limiting in the preparation methods of such a light-scattering layer and / or the fluorescent substance containing layer 7. FIG. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment. However, in the present embodiment, since the light scattering layer and / or the phosphor-containing layer 7 is provided inside the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 is formed. After that, the high refractive index layer 6 is further laminated thereon.

  Furthermore, the light guide plate 8 according to the present embodiment has the above-described configuration and the third configuration except that the light scattering layer and / or the phosphor-containing layer 7 is not provided in a part of the low refractive index layer 5. The configuration is the same as in the embodiment. Therefore, the low-refractive index layers 5 and 5 ′, the high-refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other are also laminated on the light guide plate 8 of the present embodiment. Therefore, similar to the third embodiment, it is possible to increase the thickness, to suppress cracks and peeling, and to obtain advantages such as excellent heat resistance and light resistance. Can be done.

  As shown in FIG. 8, the light guide plate 8 of the eighth embodiment has a high refractive index portion (boundary portion A) and / or a low refractive index portion (boundary portion B) 10 (high refractive index in the description of this embodiment). When the index part and the low refractive index part are pointed out without distinction, they are referred to as “boundary part 10”) that penetrates the respective layers 5, 6, 5 ′. And a desired optical waveguide is constructed in the vertical and horizontal directions of the substrate surface.

  There is no restriction | limiting in the preparation methods of such a boundary part 10. FIG. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment.

  Furthermore, the light guide plate 8 according to the present embodiment has the above-described configuration except that the light scattering layer and / or the phosphor-containing layer 7 is not provided on the upper surface of the high refractive index layer 6. The configuration is the same as in the embodiment. Therefore, since the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layers 5 and 5 ′ and the high refractive index layer 6 which are specific layers in contact with each other, the same as in the first embodiment. In addition, it is possible to obtain advantages such as being able to increase the thickness, suppressing cracks and peeling, and being excellent in heat resistance and light resistance. Further, if the boundary portion 10 is formed of the same compound as that of the specific layer, the boundary portion 10 can also be made thicker, cracks and peeling can be suppressed, heat resistance and light resistance. Advantages such as excellent properties can be obtained.

  As shown in FIG. 9, the light guide plate 8 of the ninth embodiment has a reflective layer 11 stacked on the substrate 1, and the reflective layer 11 is cylindrical or shaped so as not to cover the portion of the semiconductor light emitting device 4. A mortar-shaped hole 11H is provided. Thereby, since the light transmitted through the high refractive index layer 6 is efficiently reflected by the surface of the reflective layer 11, the light emitted from the semiconductor light emitting device 4 can be used effectively. In addition, it is also possible to provide a light scattering layer and / or a phosphor-containing layer 7 instead of the reflective layer 11.

  In addition, the light guide plate 8 according to the present embodiment has the above-described configuration and the first configuration except that the light scattering layer and / or the phosphor-containing layer 7 is not provided on the upper surface of the high refractive index layer 6. The configuration is the same as in the embodiment. Therefore, since the light guide plate 8 of the present embodiment is also configured by laminating the high refractive index layer 6 and the low refractive index layer 5 ′, which are specific layers in contact with each other, as in the first embodiment, Advantages such as being capable of thickening, suppressing cracks and peeling, and being excellent in heat resistance and light resistance can be obtained.

  As shown in FIG. 10, the light guide plate 8 of the tenth embodiment has a configuration in which a cylindrical or mortar-shaped hole 1H is formed in the substrate 1, and the semiconductor light emitting device 4 is installed at the bottom of the hole 1H. ing.

  In addition, the light guide plate 8 according to the present embodiment has the above-mentioned configuration and the configuration other than the provision of the light scattering layer and / or the phosphor-containing layer 7 in a part of the low refractive index layer 5. The configuration is the same as in the embodiment. Therefore, the light guide plate 8 of the present embodiment also includes the low refractive index layers 5 and 5 ′, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other. Therefore, similar to the first embodiment, it is possible to increase the thickness, to suppress cracks and peeling, and to obtain advantages such as excellent heat resistance and light resistance. Can be done.

As mentioned above, the specific example of the embodiment of the optical member of the present invention has been introduced. However, the first to tenth embodiments are appropriately introduced by introducing or combining a part thereof with the other embodiments. It is also possible to change.
Further, in the above-described embodiment, as long as at least two specific layers such as the low refractive index layers 5 and 5 ′, the light refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 are laminated, the conductive layer is guided. Some layers constituting the optical plate 8 may not be provided, and other layers may be further laminated. For example, since the specific layer is excellent in translucency and adhesion, it is preferable to provide a moisture-proof film formed of polyethylene terephthalate (PET) or the like on the outermost layer of the light guide plate 8 described above.

Further, the boundary portions such as the low refractive index portion 5a, the high refractive index portion 6a, and the boundary portion 10 need only penetrate at least two of the specific layers 5, 5 ′, 6, and 7, and accordingly Three or more layers may be penetrated. Furthermore, it may be formed not only of a material that can transmit light but also of a material that does not transmit light. Furthermore, you may make the boundary part contain other components, such as an inorganic particle, a fluorescent substance, a color material, for example.
The color material can be used by appropriately selecting the material and color for the purpose of improving each function of the boundary portion. For example, when two light guide layer regions that propagate different colors are separated by a boundary portion, if the boundary portion is white, the white boundary portion reflects light in each region, and light leaks to the adjacent region. It has the effect of preventing color mixing and preventing color removal. However, when the white boundary is made very thin or thin, the light shielding effect may be insufficient. In this case, if a black boundary portion is used, a loss of light guide amount due to light absorption occurs, but it is considered that light color mixing to the adjacent region can be reliably prevented.
In the case where the boundary portion contains a color material to make it white, an inorganic and / or organic material can be used as the color material. For example, as the inorganic particles, alumina fine powder, silicon oxide, aluminum oxide, titanium oxide, Metal oxides such as zinc oxide and magnesium oxide; metal salts such as calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide; boron nitride, alumina white, colloidal silica, aluminum silicate , Zirconium silicate, aluminum borate, clay, talc, kaolin, mica, and synthetic mica. Examples of the organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicon resin particles, but they are not limited to these.
In addition, in the case where the boundary portion contains a color material to be black, inorganic and / or organic materials can be used. For example, as the inorganic particles, titanium black, carbon black, iron oxide black, bismuth sulfate, etc. Is mentioned. Examples of the organic fine particles include aniline black, cyanine black, and perylene black, but are not limited to these.
Moreover, only 1 type may be used for a color material and it may use 2 or more types together by arbitrary combinations and a ratio.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, they are for the purpose of explaining the present invention, and are not intended to limit the present invention to these embodiments.

[Example 1-1]
[1-1] Production of light guide plate The light guide plate of Example 1-1 was produced according to the following procedure.

[1-1-1] Synthesis of specific layer (low refractive index layer) forming solution 1450.82 g of both-end silanol dimethyl silicone oil XC96-723 manufactured by Momentive Performance Materials Japan GK and 145 g of phenyltrimethoxysilane And 3.190 g of zirconium tetraacetylacetonate powder as a catalyst was prepared and weighed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser until the catalyst was sufficiently dissolved at room temperature for 15 minutes. Stir. Thereafter, the temperature of the reaction solution was raised to 120 ° C., and initial hydrolysis was performed while stirring at 120 ° C. under total reflux for 30 minutes.

Subsequently, nitrogen was blown in with SV20 and stirred at 120 ° C. while distilling off the generated methanol, moisture and by-product low boiling silicon components, and the polymerization reaction was further advanced for 5 hours. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

  After stopping the blowing of nitrogen and cooling the reaction solution to room temperature, the reaction solution was transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator, The low boiling silicon component was distilled off to obtain a solvent-free specific layer (low refractive index layer) forming liquid (282 mPa · s).

[1-1-2] Synthesis of specific layer (high refractive index layer) forming solution 42 g of both-end silanol dimethyl silicone oil XC96-723 manufactured by Momentive Performance Materials Japan GK, both-end silanol methyl phenyl silicone oil YF3804 98 g, 14 g of phenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonate powder as a catalyst were weighed into a three-necked Kolben equipped with a stirring blade and a condenser, and 15 g at room temperature. Stir until the minute catalyst is fully dissolved. Thereafter, the temperature of the reaction solution was raised to 120 ° C., and initial hydrolysis was performed while stirring at 120 ° C. under total reflux for 2 hours.
Subsequently, nitrogen was blown in with SV20 and stirred at 120 ° C. while distilling off the generated methanol, moisture and by-product low boiling silicon components, and the polymerization reaction was further advanced for 6 hours.
Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, then transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa for 20 minutes on an oil bath using a rotary evaporator. The low boiling silicon component was distilled off to obtain a solvent-free specific layer (high refractive index layer) forming solution.

[1-1-3] Synthesis of Specific Layer (Light Scattering Layer) Formation Solution As light scattering particles, 0.75 g of “Tospearl 145 (median particle size 5 μm)” manufactured by Momentive Performance Materials Japan GK and Al ₂ O ₃ fine CR1 specific layer described above in the (median particle size 400 nm) 0.076 g [1-1-2] (high refractive index layer) was mixed with the formation fluid 11.3g and heptane 2.5g, ultrasonic dispersion The specific layer (light scattering layer) forming liquid was obtained.

[1-1-4] Application of specific layer forming solution A low-adhesive tape manufactured by Toyo Adtec Co., Ltd. in a donut shape (periphery 10 mmφ, hole 6 mmφ) on a glass fiber reinforced epoxy laminate mounted with a blue LED so as to surround the LED portion. “T120HW” was affixed, and a 10 mmφ low adhesive tape “T120HW” was affixed immediately above this tape.
The specific layer (low refractive index layer) forming solution of [1-1-1] was spin-coated. Spin coating was performed at 300 rpm for 5 seconds and then 1200 rpm for 10 seconds.
When the above-mentioned low adhesive tape was peeled off and the specific layer forming liquid was cured at 150 ° C. for 2 hours, a low refractive index layer could be applied except for the LED portion.

Next, 0.8 ml of the specific layer (high refractive index layer) forming solution of [1-1-2] is applied to the upper surface of the low refractive index layer, and spread uniformly to 150 ° C. for 2 hours. As a result, the high refractive index layer could be provided on the low refractive index layer deficient portion including the LED and the low refractive index layer.
Next, the above-mentioned specific layer (light scattering layer) forming liquid [1-1-3] was applied to the upper surface of the high refractive index layer while flowing. Excess scattering liquid was soaked in the underlying paper. After waiting for 30 minutes or more for the scattering particles to level, the particles were cured at 150 ° C. for 2 hours.

[1-2] Analysis of each layer and evaluation method of light guide plate [1-2-1] Measurement of solid Si-NMR spectrum and calculation of silanol content For each layer of the light guide plate of Example 1-1, under the following conditions Solid Si-NMR spectrum measurement and waveform separation analysis were performed. From the obtained waveform data, the full width at half maximum of each peak was obtained for each layer of the light guide plate of Example 1-1. In addition, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Asked.

<Device conditions>
Apparatus: Chemmagnetics Infinity CMX-400 Nuclear magnetic resonance spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 Observation width: 30 kHz
Broadening factor: 20Hz

<Data processing method>
512 points were taken in as measurement data, zero-filled to 8192 points, and Fourier transformed.

<Waveform separation analysis method>
For each peak of the spectrum after Fourier transform, optimization calculation was performed by a non-linear least square method using the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.
In addition, identification of a peak is AIChE Journal, 44 (5), p. Reference was made to 1141, 1998, etc.

[1-2-2] Measurement of silicon content A single cured product of each layer (low refractive index layer, high refractive index layer, light scattering layer) of the light guide plate of Example 1-1 was pulverized to about 100 μm, and a platinum crucible. In the atmosphere, after baking at 450 ° C. for 1 hour, then at 750 ° C. for 1 hour, and at 950 ° C. for 1.5 hours to remove the carbon component, the obtained residue is more than 10 times the amount Add sodium carbonate, heat with a burner to melt, cool it, add demineralized water, adjust the pH to neutral with hydrochloric acid and adjust to a few ppm as silicon, made by Seiko Electronics ICP analysis was performed using “SPS1700HVR”.

[1-2-3] Hardness Measurement About each layer (low refractive index layer, high refractive index layer, light scattering layer) of the light guide plate of Example 1-1, A type (durometer type A) rubber hardness tester manufactured by Furusato Seiki Seisakusho The hardness (Shore A) was measured according to JIS K6253.
[1-2-4] Refractive Index Measurement Regarding the forming liquid of each layer (low refractive index layer, high refractive index layer, light scattering layer) of the light guide plate of Example 1-1, using an Abbe refractometer at 25 ° C. The refractive index was measured.

[1-2-5] Adhesiveness Evaluation Method When the one end of the coating layer (upper layer) of the light guide plate of Example 1-1 is pinched with tweezers and slowly peeled off in the perpendicular direction, the film does not easily peel off. Those that partially broke were designated as “good” and those that easily peeled off were designated as “bad”.

[1-2-6] Light extraction effect The state of light emission of the light guide plate of Example 1-1 is observed visually and / or photographed, and light is extracted uniformly from the entire desired location of the desired location. What was recognized was defined as “good”, and what was recognized that light was not uniformly extracted was defined as “bad”.

[2. Example and Comparative Example with Boundary Portions]
[2-1. Preparation of forming solution for each layer]
[2-1-1] Synthesis of specific layer (low refractive index layer) forming solution 14.50.82 g of both end silanol dimethyl silicone oil XC96-723 manufactured by Momentive Performance Materials Japan GK and 145 g of phenyltrimethoxysilane 3.190 g of zirconium tetraacetylacetonate powder was prepared. This was placed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature until the zirconium tetraacetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C. for 5 hours while nitrogen was blown into the reaction solution with SV20. Here, “SV” is an abbreviation for “Space Velocity” and refers to the blowing amount per unit time. Therefore, SV20 means blowing N ₂ of 20 times the volume of the reaction solution in one hour.
Nitrogen blowing was stopped and Kolben was once cooled to room temperature, and then the reaction solution was transferred to an eggplant type flask and distilled off under reduced pressure on an oil bath at 120 ° C. and 1 kPa for 20 minutes using a rotary evaporator. Layer) forming liquid (viscosity 282 mPa · s; hereinafter referred to as “low refractive index binder” as appropriate) was obtained.

[2-1-2] Synthesis of specific layer (high refractive index layer) forming liquid A 42 g of both-end silanol dimethyl silicone oil XC96-723 manufactured by Momentive Performance Materials Japan GK, both-end silanol methylphenyl silicone oil 98 g of YF3804, 14 g of phenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonate powder as a catalyst were prepared and weighed into a 200 ml three-necked Kolben equipped with a stirring blade and a condenser. Stir at room temperature until the zirconium tetraacetylacetonate powder is fully dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C. for 6 hours while nitrogen was blown into the reaction solution with SV20.
Nitrogen blowing was stopped and the Kolben was once cooled to room temperature, and then the reaction solution was transferred to an eggplant type flask and distilled off under reduced pressure for 20 minutes at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator.

  Into a container, 0.1 g of ultrafine silica (product name: AEROSIL # RX200) manufactured by Nippon Aerosil Co., Ltd. and 1.0 g of the reaction liquid after distillation under reduced pressure are mixed and mixed. Centrifugal defoaming was performed using a method mixer defoaming apparatus. Thereafter, the container was placed in a vacuum chamber, and a defoaming operation was further performed to obtain a specific layer (high refractive index layer) forming liquid A (hereinafter referred to as “high refractive index binder A” as appropriate).

[2-1-3] Synthesis of specific layer (high refractive index layer) forming liquid B 105 g of both-end silanol dimethyl silicone oil XC96-723 manufactured by Momentive Performance Materials Japan GK, both-end silanol methylphenyl silicone oil 35 g of YF3804, 14 g of phenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonate powder as a catalyst were prepared and weighed into a 200 ml three-necked Kolben equipped with a stirring blade and a condenser. The mixture was stirred at room temperature until the zirconium tetraacetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C. for 6.5 hours while nitrogen was blown into the reaction solution with SV20.
Nitrogen blowing was stopped and Kolben was once cooled to room temperature, and then the reaction solution was transferred to an eggplant-shaped flask and distilled off under reduced pressure on an oil bath at 120 ° C. and 1 kPa for 20 minutes using a rotary evaporator, refractive index n = 1. A high refractive index binder of 43 was obtained.
Into a container, 0.1 g of ultrafine silica (produced by Nippon Aerosil Co., Ltd., trade name: AEROSIL # RX200) as an inorganic particle and 1.0 g of the above high refractive index binder are mixed and mixed, and a rotating / revolving mixer deaerator Was used for centrifugal defoaming. Thereafter, the container was placed in a vacuum chamber and further defoamed to obtain a specific layer (high refractive index) forming liquid B (hereinafter referred to as “high refractive index binder B”) of n = 1.43.

[2-1-4] Synthesis of specific layer (weir) forming liquid B As inorganic particles in the container, 0.78 g of ultrafine silica (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130), epoxy resin (Japan epoxy) Resin, product name: Epicoat 828US) 4.98g, epoxy resin curing agent (Japan Epoxy Resin, product name: JER Epicure YLH1230) 4.24g is mixed and mixed, using a rotating / revolving mixer deaerator. Centrifugal defoaming was performed. Thereafter, the container was evacuated and further defoaming operation was performed to obtain a specific layer (weir) forming liquid B.

[2-1-5] Synthesis of specific layer (weir) forming liquid C As inorganic particles in a container, 0.55 g of ultrafine silica (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130), non-agglomerated type alumina ( Product made by Baikowski, trade name: CR1, median particle size 0.95 microns) 2.0 g, epoxy resin (made by Japan Epoxy Resin, trade name: Epicoat 828US) 4.03 g, epoxy resin curing agent (made by Japan Epoxy Resin, product) Name: JER Epicure YLH1230) 3.42 g was added and mixed, and centrifugal defoaming was performed using a rotating / revolving mixer defoaming device. Thereafter, the container was evacuated and further defoaming operation was performed to obtain a specific layer (weir) forming liquid C.

[2-1-6] Preparation of Specific Layer (High Refractive Light Scattering Layer / Low Scattering Type) Formation Solution As light scattering particles, 0.1 g of Al ₂ O ₃ fine powder “CR1 (median particle size 400 nm)” is [1. -1-2] mixed with 9.9 g of the specific layer (high refractive index layer) forming liquid (n = 1.46) described above, and using a rotating / revolving mixer defoaming device, centrifugal defoaming / mixing is performed. I did it. Thereafter, the container was evacuated and further defoamed and mixed to obtain a specific layer (high refractive light scattering layer / low scattering type) forming liquid.

[2-1-7] Preparation of specific layer (high refractive light scattering layer / medium scattering type) forming solution As light scattering particles, “Tospearl 145 (median particle size 5 μm) manufactured by Momentive Performance Materials Japan GK ”1.0 g and Al ₂ O ₃ fine powder“ CR1 (median particle size 400 nm) ”0.1 g of the specific layer (high refractive index layer) forming liquid described above in [1-1-2] (n = 1.46) The mixture was mixed with 8.9 g, and centrifugal defoaming and mixing were performed using a rotation / revolution mixer deaerator. Thereafter, the container was further evacuated and mixed in a vacuum to obtain a specific layer (high refractive light scattering layer / medium scattering type) forming liquid.

[2-1-8] Preparation of specific layer (high refractive light scattering layer / strong scattering type) forming solution As light scattering particles, “Tospearl 145 (median particle size 5 μm) manufactured by Momentive Performance Materials Japan GK 2.0 g and Al ₂ O ₃ fine powder “CR1 (median particle size 400 nm)” 0.2 g of the specific layer (high refractive index layer) forming liquid described above in [1-1-2] (n = 1.46) The mixture was mixed with 7.8 g, and centrifugal defoaming and mixing were performed using a rotation / revolution mixer deaerator. Thereafter, the container was further evacuated and mixed with a vacuum to obtain a specific layer (high refractive light scattering layer / strong scattering type) forming liquid.

[2-1-9] Preparation of specific layer (low refractive light scattering layer) forming liquid Specific layer (low refractive index layer) synthesized with 2.0 g of 2 μm spherical silica and [1-1-1] as light scattering particles ) 8.0 g of the forming liquid (n = 1.42) was mixed, and centrifugal defoaming and mixing were performed using a rotation / revolution system mixer defoaming device. Thereafter, the container was further evacuated and mixed under vacuum to obtain a liquid for forming a specific layer (low refractive light scattering layer).

[Example 2-1]
[Manufacture of light guide plate]
Drill a 2mmφ hole in a 0.43mm thick glass fiber reinforced epoxy laminate with a drill, apply a chemical resistant tape from the back side of this hole, close the hole, and then insert a high refractive index binder A into the hole from the front side. The hole was filled by injecting and holding at 150 ° C. for 1 hour to cure. Thereafter, the chemical resistant tape was peeled off.
Also, a blue LED was installed directly under the hole, and light emitted from the blue LED was transmitted to the upper part of the substrate through a high refractive index binder A that closed the hole. Specifically, a lamp in which a C460MB chip manufactured by Cree is die-bonded with epoxy silver paste on a polyphthalamide surface-mount package (3.4 mm x 2.8 mm) and wire-bonded with a gold wire has a low refractive index. A blue LED was used which was sealed with a binder and cured by holding at 90 ° C. for 1 hour, 110 ° C. for 2 hours, and 150 ° C. for 3 hours.

A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary portion was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 μm. At this time, the distance from the nozzle of the syringe to the substrate surface was 500 μm. The drawing speed was 10 cm / second. Furthermore, the pressure when extruding the specific layer (weir) forming liquid B from the syringe was set to 1.5 MPa.
Then, this was hold | maintained at 150 degreeC and atmospheric pressure for 0.5 hour in the air atmosphere, and the boundary part was hardened. As a result, a boundary portion having a height of 500 μm and a width of 1 mm and having no ridgeline was obtained.

Next, a low refractive index binder was applied to the inner part of the boundary portion on the substrate. At this time, the boundary portion acted as a weir for blocking the low-refractive index binder, and the low-refractive index binder was applied only inside the boundary portion, and did not leak outside the boundary portion. The low refractive index binder is applied so as not to cover the upper portion of the high refractive index binder A that closes the hole, and the low refractive index layer formed by the low refractive index binder transmits light transmitted through the hole. So as not to disturb.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the low refractive index binder was hardened, and the 35-micrometer-thick low-refractive-index layer was formed.

Further, a high refractive index binder A was applied to the inner part of the boundary portion on the low refractive index layer. Also at this time, the boundary portion acted as a weir for blocking the high refractive index binder A, and the high refractive index binder A was applied only inside the boundary portion, and did not leak outside the boundary portion.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the high refractive index binder A was hardened, and the high refractive index layer A with a thickness of 415 micrometers was formed.

Further, a low refractive index binder was applied to an inner portion of the boundary portion on the high refractive index layer A. Also at this time, the boundary portion acted as a weir for blocking the low refractive index binder, and the low refractive index binder was applied only to the inside of the boundary portion, and did not leak to the outside of the boundary portion.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the low refractive index binder was hardened, and the 30-micrometer-thick low-refractive-index layer was formed.
The light guide plate was manufactured as described above.

[Evaluation]
The blue LED having an emission wavelength of 460 nm was emitted from under the hole of the obtained light guide plate, and the state was observed.
Furthermore, in the same manner as in the “[1-2-5] Adhesion evaluation method”, the adhesion of each layer of the obtained light guide plate was evaluated. In Table 3 and Tables 4 and 5 to be described later, “good” indicates that the adhesion is “good”.
Further, in the same manner as in the above-mentioned “[1-2-1] Solid Si-NMR spectrum measurement and silanol content calculation”, for each layer of the obtained light guide plate, the solid Si-NMR spectrum measurement and silanol content were determined. It was measured.
Further, in the same manner as in the above-mentioned “[1-2-2] Measurement of silicon content”, the silicon content of each layer of the obtained light guide plate was measured.
Further, the hardness (Shore A) of each layer of the obtained light guide plate was measured in the same manner as in the above “[1-2-3] hardness measurement”.
Further, in the same manner as in the above “[1-2-4] Refractive index measurement”, the refractive index of each layer of the obtained light guide plate was measured.
Moreover, the haze value was measured with COH-300A made by Nippon Denshoku Industries Co., Ltd. using the air layer as a reference, using a 1 mm-thick cured product produced by the same method as the measurement of transmittance. .
The results are shown in Table 3 shown in FIG.

In addition, in the light extraction property section of Table 3, if the column “Is it emitted far away” is “○”, it means that the light emitting surface has reached the vicinity of the weir, and if “×”, it is directly above the chip. It means that only light is emitted.
Also, in the light extraction property section of Table 3, if the column “Is the whole surface shining” is “◯”, it means that the entire surface separated by the weir is emitting light, and if “△”, It means that light is emitted to an intermediate level between the LED and the boundary portion, and “x” means that only the surface near the chip emits light.
Further, in the light extraction property section of Table 3, if the column “shielding light at the boundary” is “◯”, it means that only the surface inside the boundary emits light, and if “×”, It means that light emission has reached the adjacent surface beyond the boundary.

[Example 2-2]
A light guide plate was produced in the same manner as in Example 2-1, except that the low refractive index layer was not formed on the high refractive index layer A. The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 3 shown in FIG.

[Comparative Example 2-1]
A light guide plate was produced in the same manner as in Example 2-1, except that the high refractive index layer A and the low refractive index layer on the high refractive index layer A were not formed. The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 3 shown in FIG.

[Example 2-3]
Other than having formed the boundary portion using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B, and not forming the low refractive index layer on the high refractive index layer A Manufactured the light-guide plate like Example 2-1. The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 3 shown in FIG.

[Comparative Example 2-2]
A light guide plate was produced in the same manner as in Example 2-3 except that the high refractive index layer A and the low refractive index layer on the high refractive index layer A were not formed. The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 3 shown in FIG.

[Comparative Example 2-3]
[Manufacture of light guide plate]
A blue LED chip (manufactured by Cree, trade name: C460MB290) was attached to an electrode on a glass fiber reinforced epoxy laminate having a thickness of 0.43 mm by die bonding using epoxy silver paste and wire bonding using Au wire. The high refractive index binder A was raised and applied on the LED chip, and was cured by holding at 150 ° C. for 1 hour, and the LED chip was sealed with the high refractive index layer A.

A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary portion was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe having a nozzle diameter of 570 μm. At this time, the distance from the nozzle of the syringe to the substrate surface was 650 μm. The drawing speed was 10 cm / second. Furthermore, the pressure when extruding the specific layer (weir) forming liquid B from the syringe was set to 2 MPa.
Then, this was hold | maintained at 150 degreeC and atmospheric pressure for 0.5 hour in the air atmosphere, and the boundary part was hardened. As a result, a boundary portion having a height of 500 μm and a width of 1 mm and having no ridgeline was obtained.

Next, a high refractive index binder A was applied to the inner portion of the boundary portion on the substrate. At this time, the boundary portion acted as a weir for blocking the high refractive index binder A, and the high refractive index binder A was applied only to the inside of the boundary portion and did not leak to the outside of the boundary portion.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the high refractive index binder A was hardened, and the 500-micrometer-thick high refractive index layer A was formed.

The obtained light guide plate was evaluated by turning on the LED of the substrate in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.
It should be noted that, in the light extraction property section of Table 4, if the column of “Is it emitted far away” is “◯”, it means that the light emitting surface has reached the vicinity of the weir, and if “△”, LED and It means that the light is emitted to the middle of the boundary, and “x” means that light is emitted only directly above the chip.
Also, in the light extraction property section of Table 4, if the column “Is the whole surface shining” is “◯”, it means that the entire surface separated by the weir is emitting light, and if “△”, It means that light is emitted to an intermediate level between the LED and the boundary portion, and “x” means that only the surface near the chip emits light.
Furthermore, in the light extraction property section of Table 4, if the column of “shielding light at the boundary” is “◯”, it means that only the surface inside the boundary emits light, and if “×”, It means that light emission has reached the adjacent surface beyond the boundary.

[Example 2-4]
The LED chip is sealed with a low refractive index layer, and instead of the high refractive index layer A, a low refractive index layer is formed in the same manner as in Example 2-1, and on the low refractive index layer, A light guide plate was produced in the same manner as Comparative Example 2-3 except that the light scattering layer was formed in the following manner.
For the light scattering layer, a specific layer (low refractive light scattering layer) forming liquid is applied to the inner part of the boundary portion on the low refractive index layer, and this is held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour. And cured. At this time, the thickness of the light scattering layer was 470 μm. In this case as well, the boundary part acts as a weir to dam the specific layer (low refractive light scattering layer) forming liquid, and the specific layer (low refractive light scattering layer) forming liquid is applied only inside the boundary part, There was no leakage outside the section.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.

[Example 2-5]
The height of the weir is 500 μm, and instead of the high refractive index layer A, a low refractive index layer having a thickness of 30 μm is formed on the substrate in the same manner as in Example 2-1, and the top of the low refractive index layer is formed. A light guide plate was produced in the same manner as in Comparative Example 2-3 except that the high refractive index layer B was formed in the following manner.
For the high refractive index layer B, a high refractive index binder B is applied to the inner part of the boundary portion on the low refractive index layer, and this is cured by holding it at 150 ° C. and atmospheric pressure for 1 hour in an air atmosphere. Formed. At this time, the thickness of the high refractive index layer B was 470 μm. In this case as well, the boundary portion acted as a weir for blocking the high refractive index binder B, and the high refractive index binder B was applied only to the inside of the boundary portion and did not leak out to the outside of the boundary portion.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.

[Example 2-6]
Using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B, forming the low refractive index layer in the same manner as in Example 2-1, instead of the high refractive index layer A, The high refractive index layer A was formed on the low refractive index layer in the same manner as in Example 2-1, and the specific layer (low refractive light scattering layer) forming liquid was formed on the high refractive index layer A. In the same manner as in Example 2-3 except that a light scattering layer was formed in the same manner as in Example 2-4 except that a specific layer (high refractive light scattering layer / low scattering type) forming solution was used instead of The light guide plate was manufactured.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.

[Example 2-7]
Using specific layer (weir) forming liquid B instead of specific layer (weir) forming liquid C, forming specific layer (high refractive light scattering layer / strong scattering type) instead of specific layer (low refractive light scattering layer) forming liquid A light guide plate was produced in the same manner as in Example 2-6 except that the liquid was used.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.

[Example 2-8]
In the same manner as in Example 2-7, except that the specific layer (high refractive light scattering layer / medium scattering type) forming liquid was used instead of the specific layer (high refractive light scattering layer / strong scattering type) forming liquid. A light plate was manufactured.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 4 shown in FIG.

[Example 2-9]
[Manufacture of light guide plate]
A blue LED (trade name: C460MB290, manufactured by Cree Inc.) was attached to an electrode on a glass fiber reinforced epoxy laminated substrate having a thickness of 0.43 mm by die bonding using an epoxy silver paste and wire bonding using Au wire. This LED was sealed in a dome shape with a high refractive index binder A, and held at 150 ° C. for 1 hour to be cured.

A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid C. The boundary portion was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 μm. At this time, the distance from the nozzle of the syringe to the substrate surface was 350 μm. The drawing speed was 15 cm / second. Furthermore, the pressure when extruding the specific layer (weir) forming liquid C from the syringe was set to 4 MPa.
Then, this was hold | maintained at 150 degreeC and atmospheric pressure for 0.5 hour in the air atmosphere, and the boundary part was hardened. As a result, a boundary portion having a height of 300 μm and a width of 1.3 mm and having no ridgeline was obtained.

Subsequently, the low refractive index layer and the high refractive index layer A were formed in the inner part of the said boundary part on a board | substrate similarly to Example 2-1. Example 2-4 was used except that a specific layer (high refractive light scattering layer / strong scattering type) forming liquid was used on the high refractive index layer A instead of the specific layer (low refractive light scattering layer) forming liquid. A light scattering layer was formed in the same manner as described above to produce a light guide plate.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

In the light extraction property section of Table 5, if the column “Is it emitted far away” is “○”, it means that the light emitting surface has reached the vicinity of the weir, and if “×”, it is directly above the chip. It means that only light is emitted.
In addition, in the light extraction property section of Table 5, if the column “Is the whole surface shining” is “◯”, it means that the entire surface separated by the weir is emitting light, and if “×”, It means that only the surface near the chip emits light.
Further, in the light extraction property section of Table 5, if the column of “shielding light at the boundary” is “◯”, it means that only the surface inside the boundary emits light, and if “×”, It means that light emission has reached the adjacent surface beyond the boundary.

[Example 2-10]
A light guide plate was produced in the same manner as in Example 2-9 except that the drawing speed when forming the boundary was 24 cm / sec. As a result, a light guide plate having a boundary portion having a height of 150 μm and a width of 0.6 mm and having no ridgeline was obtained.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

[Example 2-11]
A light guide plate was produced in the same manner as in Example 2-9, except that the boundary portion was formed using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

[Example 2-12]
Example 2-9 except that the specific layer (weir) forming liquid B was used instead of the specific layer (weir) forming liquid C, and that the drawing speed when forming the boundary portion was 9 cm / sec. Similarly, a light guide plate was manufactured.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

[Example 2-13]
A light guide plate was produced in the same manner as in Example 2-9 except that the high refractive index layer A was formed directly on the substrate without forming the low refractive index layer, and the light scattering layer was formed thereon.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

[Example 2-14]
A light guide plate was produced in the same manner as in Example 2-9 except that the light scattering layer was not formed.
The obtained light guide plate was evaluated in the same manner as in Example 2-1. The results are shown in Table 5 shown in FIG.

[Summary]
From Tables 3 to 5 shown in FIG. 11 to FIG. 13, the light guide enhanced by the lamination of layers having different refractive indexes is excellent in the light guiding function to the distance, and the light extraction surface provided with the scattering layer is the surface. It can be seen that it is excellent in uniform light emission (light extraction). Furthermore, even if the light guide layers having different emission colors are adjacent to each other by providing a boundary portion, the colors are shielded and do not mix, and if necessary, the boundary portion is made white so that the boundary portion can be in the light guide surface. As a result, the light emission uniformity in the vicinity of the boundary, which tends to be the darkest farthest from the LED, could be improved. Even when the laminated specific layer was a thin film having a total thickness of 120 μm, the in-plane light emission uniformity was not deteriorated, and an extremely thin light guide layer could be formed. As described above, a light guide layer capable of uniformly emitting light with a simple structure can be formed by stacking layers having different refractive indexes and using the scattering layer / boundary layer together.

[3] Manufacture of light guide plate [3-1] Preparation of forming liquid for each layer [3-1-1] Preparation of specific layer (low refractive index layer) forming liquid A (low refractive index; n = 1.41) 390 g of Silanol Dimethyl Silicone Oil XC96-723 at both ends made by Momentive Performance Materials Japan GK, 10.41 g of methyltrimethoxysilane, and 0.280 g of zirconium tetraacetylacetonate powder as a catalyst, stirring blade Were weighed into a 500 ml three-necked Kolben equipped with a fractionating tube, a Dimroth condenser and a Liebig condenser, and stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux.

Subsequently, the distillate was connected to the Liebig condenser side, nitrogen was blown into the liquid with SV20, and methanol, water, and low-boiling silicon components of by-products were distilled off with nitrogen accompanying at 100 ° C. and 500 rpm for 1 hour. Stir. Subsequently, the nitrogen flow rate was increased to SV40 and the polymerization reaction was continued for 4.7 hours while the temperature was raised and maintained at 130 ° C. while blowing into the liquid to obtain a reaction liquid having a viscosity of 158.7 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

  After stopping the blowing of nitrogen and cooling the reaction solution to room temperature, the reaction solution was transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator, The low boiling silicon component was distilled off to obtain a solvent-free liquid having a viscosity of 260 mPa · s.

  In a glass screw tube bottle, 10 g of this solution and 0.04 g of zirconium tetraacetylacetonate powder were weighed and dissolved by stirring in an oil bath at 100 ° C. for 5 minutes (hereinafter referred to as “low refractive index binder A” as appropriate). 2g of low refractive index binder A solution after transparent dissolution, 0.194g of hydrophobic fumed silica RX200 manufactured by Nippon Aerosil Co., Ltd. is weighed into an ointment jar, and using a rotating / revolving mixer deaerator for 3 minutes in mixing mode The mixture was stirred for 1 minute in the defoaming mode to obtain a specific layer (low refractive index layer) forming liquid A (low refractive index; n = 1.41).

[3-1-2] Preparation of Specific Layer (Low Refractive Index Layer) Formation Liquid B (Low Refractive Index; n = 1.42) Momentive Performance Materials Japan Godo Kaisha Silanol Dimethyl Silicone Oil XC96 1450.82 g of -723, 145 g of phenyltrimethoxysilane, and 3.190 g of zirconium tetraacetylacetonate powder were prepared. This was placed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature until the zirconium tetraacetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

  Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C. for 5 hours while nitrogen was blown into the reaction solution with SV20. After the nitrogen blowing was stopped and the Kolben was once cooled to room temperature, the reaction solution was transferred to an eggplant-shaped flask and distilled under reduced pressure on an oil bath at 120 ° C. and 1 kPa for 20 minutes using a rotary evaporator, and no viscosity of 282 mPa · s was obtained. A solvent solution was obtained.

  In a glass screw tube bottle, 10 g of this solution and 0.06 g of zirconium tetraacetylacetonate powder were weighed and stirred for 5 minutes at 100 ° C. in an oil bath (hereinafter referred to as “low refractive index binder B” as appropriate). 2g of low refractive index binder B solution after transparent dissolution, 0.196g of hydrophobic fumed silica RX200 manufactured by Nippon Aerosil Co., Ltd. is weighed into an ointment jar, using a rotating / revolving mixer defoaming device, 3 minutes in mixing mode The mixture was stirred for 1 minute in the defoaming mode to obtain a specific layer (low refractive index layer) forming liquid B (low refractive index; n = 1.42).

[3-1-3] Preparation of Specific Layer (High Refractive Index Layer) Formation Liquid C (High Refractive Index; n = 1.46) Momentive Performance Materials Japan GK End Silanol Dimethyl Silicone Oil XC96 42 g of -723, 98 g of silanol methylphenyl silicone oil YF3804 at both ends, 14 g of phenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonate powder as a catalyst were prepared, and a stirring blade and a condenser were attached. Weighed in a three-necked Kolben and stirred at room temperature for 15 minutes until the catalyst was fully dissolved. Thereafter, the temperature of the reaction solution was raised to 120 ° C., and initial hydrolysis was performed while stirring at 120 ° C. under total reflux for 2 hours.
Subsequently, nitrogen was blown in with SV20 and stirred at 120 ° C. while distilling off the generated methanol, moisture and by-product low boiling silicon components, and the polymerization reaction was further advanced for 6 hours.
Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, then transferred to an eggplant-shaped flask, and methanol and moisture remaining in a minute amount at 120 ° C. and 1 kPa for 20 minutes on an oil bath using a rotary evaporator. The low boiling silicon component was distilled off to obtain a solvent-free liquid having a viscosity of 150 mPa · s.

  In a glass screw tube bottle, 10 g of this solution and 0.08 g of zirconium tetraacetylacetonate powder were weighed and stirred and dissolved in an oil bath at 100 ° C. for 5 minutes (hereinafter referred to as “high refractive index binder C” as appropriate). 2g of high refractive index binder C solution after transparent dissolution, 0.175g of hydrophobic fumed silica RX200 manufactured by Nippon Aerosil Co., Ltd. is weighed in an ointment jar, and using a rotating / revolving mixer deaerator for 3 minutes in mixing mode The mixture was stirred for 1 minute in a defoaming mode to obtain a specific layer (high refractive index layer) forming liquid C (high refractive index; n = 1.46).

[3-1-4] Preparation of Specific Layer (High Refractive Index Light Scattering Layer) Formation Liquid D 5 g of Specific Layer (High Refractive Index Layer) Formation Liquid C of [3-1-3], light scattering particles For mixing 0.11 g of Al ₂ O ₃ fine powder “CR-1 (median particle size 400 nm)” and 1.09 g of “Tospearl 145 (median particle size 5 μm)” manufactured by Momentive Performance Materials Japan GK A specific layer (high refractive index light scattering layer) forming liquid D was obtained by weighing in a container, performing centrifugal defoaming and mixing using a rotating / revolving mixer defoaming device.

[3-2] Preparation of Boundary (Weir) Formation Liquid [3-2-1] Preparation of Boundary (Weir) Formation Liquid A (White Condensation Type Silicone Resin) Low Refractive Index of [3-1-2] 4.2 g of binder B liquid, 1.407 g of Al ₂ O ₃ fine powder “CR-1 (median particle size 400 nm)” as light scattering particles, 1.302 g of hydrophobic fumed silica Aerosil RX200 manufactured by Nippon Aerosil Co., Ltd. Was measured in a mixing container and subjected to centrifugal defoaming / mixing using a rotating / revolving mixer defoaming device to obtain a white boundary (weir) forming liquid A.

[3-2-2] Preparation of boundary part (weir) forming liquid B (white addition type silicone resin) 2.0 g of silicone resin OE6336-A liquid manufactured by Toray Dow Corning Co., Ltd. As light-scattering particles, 0.8 g of Al ₂ O ₃ fine powder “CR-1 (median particle size 400 nm)” and 0.7 g of hydrophobic fumed silica Aerosil RX200 manufactured by Nippon Aerosil Co., Ltd. are weighed into a mixing container and rotated. -Centrifugal defoaming and mixing were performed using a revolution-type mixer defoaming device to obtain a white boundary (weir) forming liquid B.

[3-2-3] Preparation of boundary (weir) forming solution C (black addition type silicone resin) 2.5 g of silicone resin OE6336-A solution manufactured by Toray Dow Corning Co., Ltd. As a black pigment, 1.5 g of Mitsubishi Materials titanium black particles BM-C are weighed in a mixing container, and subjected to centrifugal defoaming and mixing using a rotating / revolving mixer defoaming device. ) A forming liquid C was obtained.

[3-2-4] Preparation of Boundary (Weir) Formation Liquid D (White Condensation Type Silicone Resin: Low Viscosity) 15 g of low refractive index binder B liquid of [3-1-2] as light scattering particles , 4.32 g of Al ₂ O ₃ fine powder “CR-1 (median particle size 400 nm)” and 2.8 g of hydrophobic fumed silica Aerosil RX200 manufactured by Nippon Aerosil Co., Ltd. are weighed into a mixing container, and a rotating / revolving mixer Centrifugal defoaming / mixing was performed using a defoaming device to obtain a white boundary portion (weir) forming liquid D.

[4] Description of operation and evaluation of specific examples [Example 3-1]
An example of manufacturing a light-emitting device having a weir and having a coating-type light guide layer is described below.
[Manufacture of light guide plate]
A wiring board provided with a recess for installing the LED in the center and coated with a white solder paste on a portion other than the recess was prepared. A reflector is attached to the recess.
A green LED was mounted in the recess. Next, the boundary part was drawn on this board | substrate using the boundary part (weir) formation liquid A obtained by [3-2-1]. The boundary portion was drawn to be a weir surrounding the green LED. Moreover, drawing of the boundary part was performed using Musashi Engineering Co., Ltd. pressure air type dispenser, and using the company's taper nozzle TPN-22G (inner diameter 0.4mm). The drawing speed at this time was 2 mm / second. Furthermore, the pressure at the time of extruding the boundary part (weir) formation liquid A from a syringe was set to 0.364 MPa.
Then, this was hold | maintained at 150 degreeC and atmospheric pressure for 1.0 hour in the air atmosphere, and the boundary part was hardened. As a result, a boundary portion having a height of about 300 μm and having no ridgeline was obtained.

Next, the specific layer (low refractive index layer) forming liquid A was applied to the inner part of the boundary portion on the substrate using a dispenser. Here, the boundary portion acts as a weir for blocking the specific layer (low refractive index layer) forming liquid A, and the specific layer (low refractive index layer) forming liquid A is applied only inside the boundary portion, and outside the boundary portion. Did not leak. Further, the specific layer (low refractive index layer) forming liquid A is applied to the concave portions on the wiring board so as not to enter, and the low refractive index layer formed by the specific layer (low refractive index layer) forming liquid A is formed into the concave portions. The transmission of light transmitted through is not disturbed.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the specific layer (low-refractive-index layer) formation liquid A was hardened, and the low-refractive-index layer about 50 micrometers thick was formed.

Furthermore, the specific layer (low refractive index layer) forming liquid B was applied onto the low refractive index layer inside the boundary using a dispenser. Also in this case, the boundary part acts as a weir for blocking the specific layer (low refractive index layer) forming liquid B, and the specific layer (low refractive index layer) forming liquid B is applied only inside the boundary part. It did not leak outside.
And this was hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in air atmosphere, the specific layer (low refractive index layer) formation liquid B was hardened, and the high refractive index layer about 200 micrometers thick was formed.

Furthermore, the specific layer (high refractive index light scattering layer) forming liquid D was applied onto the high refractive index layer inside the boundary using a dispenser. Also at this time, the boundary portion acts as a weir for blocking the specific layer (high refractive index light scattering layer) forming liquid D, and the specific layer (high refractive index light scattering layer) forming liquid D is applied only inside the boundary portion. , Did not leak outside the boundary.
And this is hold | maintained at 150 degreeC and atmospheric pressure for 1 hour in an air atmosphere, the specific layer (high refractive index light-scattering layer) formation liquid D is hardened, and a high refractive index light-scattering layer about 50 micrometers thick is formed. did.
As described above, a light emitting device having a coating type light guide layer as schematically shown in FIG. 14 was manufactured.

[Evaluation]
The light emitting device having the coated light guide layer thus obtained was energized to cause the green LED to emit light, and the state was observed.
Furthermore, the solid Si-NMR spectrum, silanol content, silicon content, hardness (Shore A), and adhesion evaluation were measured for each layer of the obtained light guide plate in the same manner as in Example 1-1.

Moreover, the refractive index of each layer of the light guide plate was measured as follows.
[Refractive index measurement]
The refractive index of the specific layer can be measured by a known method such as a immersion method (solid object), a Pluffich refractometer, an Abbe refractometer, a prism coupler method, an interference method, and a minimum deflection angle method. Each layer of this example has very little change in refractive index before and after curing. Therefore, the Abbe refractometer (sodium D line (589 nm)) in the liquid state before curing was used for each layer of the light guide plate of Example 3-1 (sodium D line (589 nm)). The formation liquid refractive index of the low refractive index layer, the high refractive index layer, and the light scattering layer was measured.

Moreover, the haze value of each layer of the light guide plate was measured as follows.
[Haze value evaluation method]
A single cured film having a smooth surface with a thickness of about 1 mm without scattering due to scratches and unevenness is prepared. Using this single cured film, the air layer is used as a reference, and COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. The haze value was measured.

The results are shown in Table 6.
In Table 6, those having good adhesion in the adhesion evaluation results are indicated by “◯”.
In addition, in the light extraction property section of Table 6, if the column “Is it shining far” is “◯”, it means that the light-emitting surface has reached the vicinity of the weir, and if “△”, LED and This means that the light emitting surface has reached the vicinity of the middle of the weir. If it is “x”, it means that light is emitted only directly above the chip.
In addition, in the light extraction property section of Table 6, if the column “Is the whole surface shining” is “◯”, it means that the entire surface separated by the weir is emitting light, and if “△”, It means that light is emitted to an intermediate level between the LED and the boundary portion, and “x” means that only the surface near the chip emits light.
Further, in the light extraction property section of Table 6, if the column of “shielding light at the boundary” is “◯”, it means that only the surface inside the boundary emits light, and if “×”, It means that light emission has reached the adjacent surface beyond the boundary.

[Example 3-2]
The light emitting device of Example 3-2 was manufactured in the same manner as in Example 3-1, except that the specific layer (low refractive index layer) forming liquid B was used as the low refractive index layer forming liquid. Evaluation similar to 1 was performed. The results are shown in Table 6.

[Understanding from Examples 3-1 and 3-2]
Even if the weir material was a silicone resin, the light guide layer could be suitably formed without peeling the weir and the light guide layer. In addition, Example 3-1, in which the difference in refractive index between the high refractive index layer and the low refractive index layer is larger than that of Example 3-2, has improved light propagation efficiency compared to Example 3-2 and is more uniform than LED. I was able to emit light.

[5] Other Examples of Weir Production and Evaluation [5-1] Drawing and Curing of Weir [5-1-1] White Weir (Addition Type Silicone Resin)
Using the white boundary (weir) forming liquid B obtained in [3-2-2], a square weir with a side of 1 cm was drawn on the slide glass. The weir was drawn using a pneumatic dispenser manufactured by Musashi Engineering Co., Ltd. and a taper nozzle TPN-22G (inner diameter 0.4 mm) manufactured by the same company. The drawing speed at this time was 3 mm / second. Furthermore, the pressure at the time of extruding the boundary part (weir) formation liquid B from a syringe was set to 150 kPa.
Then, this was hold | maintained at 150 degreeC and atmospheric pressure for 1.0 hour in air atmosphere, and the weir was hardened. As a result, a white weir having a height of about 300 μm and having no ridgeline was obtained.

[5-1-2] Black weir (addition type silicone resin)
The weir was drawn in the same manner as [5-1-1] except that the black boundary portion (weir) forming liquid C obtained in [3-2-3] was used on the slide glass. As a result, a black weir having a height of about 300 μm and having no ridgeline was obtained.

[5-2] Evaluation of weirs We applied stress to the glass slides that were only drawn and hardened on the weirs and divided them into two parts, and observed the shape of the fractured surface of the weirs with a stereomicroscope to examine the height and cross-sectional structure of the weirs. . Regarding the weir of [5-1-1], a low refractive index layer, a high refractive index layer, and a light scattering layer were laminated and cured inside the weir in the same manner as in Example 3-1, and this was broken, The fracture surface was observed with a microscope, and the adhesion and wettability between the weir and the light guide layer material were examined.

[5-3] Functions of Various Weirs From the experimental examples of Example 3-1, [5-1-1], and [5-1-2], both the condensation type silicone resin and the addition type silicone resin are preferably used. It was found that it can be formed. In addition, the weir formed of any resin had good adhesion to the specific layer forming the light guide layer, and the interface between the weir and the specific layer was not peeled off, and no repelling occurred when the specific layer was applied. It was also found that the weir can be colored white or black.

  When two light guide layer areas that propagate different colors are separated by a weir, if the weir is white, the white weir reflects the light in each area, preventing leakage of light to the adjacent area, and color mixing There is an effect to prevent. However, when the white weir is made very thin or thin, the light shielding effect may be insufficient. In this case, if a black weir is used, the amount of guided light is lost due to light absorption. However, it is considered that the color mixture of light to the adjacent region can be surely prevented.

The optical member of the present invention can be thickened, the occurrence of cracks in the thick film portion is suppressed, the peeling from the substrate and the peeling on the laminated surface are suppressed, and the heat resistance and light resistance are excellent. There is an effect.
The optical waveguide and light guide plate formed using the optical member of the present invention have a high degree of freedom in designing the film thickness, and the occurrence of cracks is suppressed even in the thick film part, and peeling from the substrate and peeling on the laminated surface are prevented. It is suppressed and has an effect of being excellent in heat resistance and light resistance.

  Therefore, the optical member, the optical waveguide, and the light guide plate of the present invention have extremely high industrial applicability in the respective fields.

It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a schematic sectional drawing which shows embodiment of the light-guide plate using the optical member of this invention. It is a table | surface which shows the result of Examples 2-1 to 2-3 of this invention, and Comparative Examples 2-1 and 2-2. It is a table | surface which shows the result of Examples 2-4 to 2-8 of this invention, and Comparative Example 2-3. It is a table | surface which shows the result of Examples 2-9 to 2-14 of this invention. It is typical sectional drawing of the light-emitting device produced in Example 3-1 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 1H, 5H Hole 2 Semiconductor light emitting element 3 Sealing material 4 Semiconductor light emitting device 5 Low refractive index layer 5a Low refractive index part 6 High refractive index layer 6a High refractive index part 7 Light scattering layer and / or phosphor containing layer 8 Optical member (light guide plate)
9 Angle formed by the side surface and the laminated surface of the optical member 10 High refractive index portion and / or low refractive index portion (boundary portion)
11 Reflective layer

Claims (15)

An optical member in which two or more layers having different refractive indexes are laminated,
An optical member characterized in that at least two layers in contact with each other satisfy the following conditions.
(1) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.
(4) Hardness measurement value (Shore A) by durometer type A is 5 or more and 90 or less. An optical member in which two or more layers having different refractive indexes are laminated,
An optical member characterized in that at least two layers in contact with each other satisfy the following conditions.
(5) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.5 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 1.0 ppm to 5.0 ppm. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less. The optical member according to claim 1 or 2, wherein a refractive index of at least one of the layers in contact with each other is 1.45 or more. The refractive index of at least one layer of the layers in contact with each other is 1.45 or more, and the refractive index of at least one other layer is less than 1.45. The optical member described. An optical member in which two or more layers having different haze values are laminated,
An optical member characterized in that at least two layers in contact with each other satisfy the following conditions.
(1) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less.
(4) Hardness measurement value (Shore A) by durometer type A is 5 or more and 90 or less. An optical member in which two or more layers having different haze values are laminated,
An optical member characterized in that at least two layers in contact with each other satisfy the following conditions.
(5) In the solid Si-nuclear magnetic resonance spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.5 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 1.0 ppm to 5.0 ppm. .
(2) The silicon content is 10% by weight or more.
(3) The silanol content is 0.01% by weight or more and 10% by weight or less. The optical member according to claim 5, wherein at least one of the layers in contact with each other has a haze value of 50 or more. The optical member according to claim 1, wherein at least one of the layers in contact with each other contains inorganic particles. The optical member according to claim 8, wherein the median particle diameter of the inorganic particles is 1 to 10 nm. At least one of the layers in contact with each other contains inorganic particles having a median particle size of 0.05 to 50 μm, and the layer and / or at least one other layer contains inorganic particles having a median particle size of 1 to 10 nm. The optical member according to any one of claims 5 to 7, wherein: The optical member according to any one of claims 1 to 10, wherein at least one of the layers in contact with each other contains a phosphor. The optical member according to any one of claims 1 to 11, wherein an angle formed between the side surface and the laminated surface of the optical member is 30 degrees or more and 80 degrees or less. The optical member according to any one of claims 1 to 12, further comprising a boundary portion penetrating at least two of the layers in contact with each other. An optical waveguide formed using the optical member according to claim 1. A light guide plate formed using the optical member according to claim 1.

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