JP2005213453A - Radiation hardening resin composition and method for producing radiation hardening resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation hardening resin composition having excellent transparency, storage stability and the like. <P>SOLUTION: One hundred parts by weight (pts. wt.) of silica particles are treated with ≥ 20 pts.wt. of a silane coupling agent at a temperature of ≥70°C to prepare silane-treated silica particles. Then, the treated particles are mixed with a monomer bearing a radiation hardening group and/or an oligomer thereof to provide the radiation hardening resin composition. This resin composition includes largely decreased residue of unreacting silane coupling agent and shows high transparency and storage stability. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a radiation curable resin composition and the like, and more particularly to a radiation curable resin composition having both excellent storage stability and transparency.

Radiation curable resin compositions that undergo a curing reaction by irradiation with radiation such as ultraviolet rays and electron beams are widely used in various applications such as various coating materials, adhesive materials, and optical materials. In such applications, in recent years, high adhesion, high surface hardness, low linear expansion coefficient (dimensional stability), low curing shrinkage, low water absorption, high gas barrier properties, high elastic modulus, high heat resistance or high compression Higher characteristics are required in terms of strength and the like.
In particular, a technique is known in which a filler such as silica particles is blended into a radiation curable resin composition for the purpose of improving high surface hardness, high heat resistance, and mechanical properties. In this case, in order to prevent sedimentation or aggregation of the filler, a method of coating the filler with a surfactant, a silane coupling agent, or the like is performed. For example, silica particles coated with the silane coupling agent and curability are used. The example which used the composition containing resin for optical materials is given (refer patent document 1).

Japanese Patent Laid-Open No. 03-014880

By the way, transparency in materials such as optical materials is required. For this reason, when reacting a filler such as silica particles with a silane coupling agent, in order to avoid a decrease in transparency of the radiation curable resin composition due to aggregation or gelation of the silica particles, The reaction conditions are as low as possible and as long as possible.
However, a long reaction time is not practical, and there is a problem that the storage stability of the radiation curable resin composition prepared under the reaction conditions conventionally performed is insufficient.
In addition, when using a filler having a particle diameter equal to or smaller than the wavelength of visible light, such as an ultrafine particle filler, it is particularly easy to cause sedimentation and aggregation of the filler, and it is difficult to maintain the transparency of the composition. Many. Furthermore, even when the transparency of the composition is ensured, there is a problem that the storage stability of the composition is significantly reduced.

Thus, the present invention has been made to meet the demands that arise when developing radiation curable resin compositions.
That is, an object of the present invention is to provide a radiation curable resin composition excellent in transparency and storage stability.
Another object of the present invention is to provide a method for producing a radiation curable resin composition having excellent transparency and storage stability.
Furthermore, another object of the present invention is to provide a cured product having optically excellent transparency and excellent in high surface hardness, substrate adhesion and the like.
Another object of the present invention is to provide an optical material which is excellent in optical transparency, excellent in high surface hardness, substrate adhesion and the like.
Furthermore, another object of the present invention is to provide a laminate excellent in transparency, high surface hardness, substrate adhesion and the like.
Another object of the present invention is to provide an optical recording medium that is optically excellent.

In order to solve this problem, in the present invention, silica particles prepared from silica particles and a silane coupling agent under specific reaction conditions are used.
That is, the radiation curable resin composition to which the present invention is applied includes the silane-treated silica particles surface-treated by reacting 20 parts by weight or more of the silane coupling agent with 100 parts by weight of the silica particles, and the radiation curable resin composition. And a monomer having a group and / or an oligomer thereof, wherein the amount ratio (A) of the unreacted silane coupling agent represented by the following formula is 6% or less.

In the radiation curable resin composition to which the present invention is applied, the amount ratio (A) of the unreacted silane coupling agent is 6% or less, while ensuring the transparency of the radiation curable resin composition, High storage stability is obtained.
In the radiation curable resin composition to which the present invention is applied, the content of silane-treated silica particles having a particle size of more than 30 nm in the composition is preferably 1% by weight or less.
Further, in the radiation curable resin composition to which the present invention is applied, if the silica particles are obtained by hydrolysis reaction of an oligomer of alkoxysilane, such silica particles are small particles. Since it exhibits a diameter and a property that hardly aggregates, a radiation-curable resin composition having high transparency can be obtained.

  Furthermore, in the radiation curable resin composition to which the present invention is applied, the silane coupling agent is a compound represented by the following formula (1). The hydroxy group on the surface of the silica particles forms a Si—O—Si bond through a dealcoholization reaction, and the surface of the silica particles can be sufficiently covered with the silane coupling agent.

(In formula (1), R is an alkyl group, R ′ is a group containing a reactive group, and Q ¹ and Q ² are each independently a monovalent organic group.)

Next, the present invention has a step of preparing silane-treated silica particles by reacting 20 parts by weight or more of a silane coupling agent with respect to 100 parts by weight of silica particles at a temperature of 70 ° C. or more. The gist of the production method of the curable resin composition.
According to the method for producing a radiation curable resin composition to which the present invention is applied, the reaction between the silica particles and the silane coupling agent is promoted, and the residual amount of the unreacted silane coupling agent in the composition is greatly increased. Can be reduced. As a result, transparency of the prepared radiation curable resin composition is ensured and high storage stability is obtained.

Next, by curing the radiation curable resin composition to which the present invention is applied, a cured product having optically excellent transparency and excellent in high surface hardness, substrate adhesion and the like is obtained.
In addition, the cured product to which the present invention is applied can be used as an optical material because it has excellent optical transparency, high surface hardness, and excellent substrate adhesion.
Furthermore, the laminated body excellent in transparency, high surface hardness, base material adhesiveness, etc. is obtained by laminating | curing the hardened | cured material to which this invention is applied on a predetermined | prescribed board | substrate.
Further, by having a layer made of a cured product to which the present invention is applied, an optically excellent optical recording medium is provided.

  Thus, according to the present invention, a radiation curable resin composition excellent in transparency and storage stability can be obtained.

Hereinafter, embodiments for carrying out the present invention will be described in detail based on representative examples.
(Silica particles)
The silica particles used in the present embodiment are derived and synthesized from raw materials such as alkoxysilanes in addition to silica particles dispersed in industrially sold solvents, silica particles in powder form, and the like. And silica particles. Among these, silica particles derived or synthesized from raw materials such as silica particles and alkoxysilanes dispersed in a solvent are more preferable because of easy mixing and dispersion as a radiation curable resin composition. Here, silica refers to silicon oxide in general, and it does not matter whether the ratio of silicon and oxygen is crystalline or amorphous.

In the present embodiment, the silica particles are preferably ultrafine particles, and the lower limit of the number average particle diameter is preferably 0.5 nm or more, more preferably 1 nm or more. When the number average particle size is excessively small, the cohesiveness of the ultrafine particles is extremely increased, and the transparency and mechanical strength of the cured product may be extremely decreased, or the characteristics due to the quantum effect may not be remarkable. The upper limit is preferably 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less, particularly preferably less than 15 nm, and most preferably 12 nm or less.
Moreover, it is preferable that the particle size of a silica particle is small. Specifically, the content of silica particles preferably having a particle size of 30 nm or more, more preferably the content of silica particles having a particle size of 15 nm or more, is preferably 1% by weight or less, more preferably based on the radiation curable resin composition. Is 0.5% by weight or less. Or it is 1 volume% or less with respect to hardened | cured material, More preferably, it is 0.5 volume% or less. A large content of silica particles having a large particle size is not preferable because light scattering increases, and the transmittance decreases.

  The number average particle diameter of the silica particles is measured from a transmission electron microscope (TEM) observation image. That is, the diameter of a circle having the same area as the observed ultrafine particle image is defined as the particle size of the silica particle image. For example, when the number average particle diameter is calculated by a known statistical processing technique for image data using the measured particle diameter, it is desirable that the number of ultrafine particle images (number of statistical processing data) used for statistical processing is as large as possible. . For example, in terms of reproducibility, the number of silica particle images randomly selected is 50 or more, preferably 80 or more, and more preferably 100 or more. Calculation of the volume% in hardened | cured material is converted with the volume of the ball | bowl which makes the particle size calculated by the method mentioned above a diameter.

  As the silica particles dispersed in the solvent, for example, those having a solid content of 10 wt% to 40 wt% can be used. Specific examples of the dispersion medium include, for example, alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol; glycols such as ethylene glycol; esters such as ethyl cellosolve; amides such as dimethylacetamide; xylene Hydrocarbons such as: ketones; ethers; and mixtures thereof, among which isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, and mixtures thereof are compatible with organic components. Is preferable from the viewpoint of the transparency of the resulting cured product. In addition, as a silica particle, what surface-treated with surface treating agents, such as surfactant and a silane coupling agent, can be used. By using the surface treatment agent, aggregation and particle coarsening can be prevented, and a highly dispersed and transparent radiation curable resin composition can be obtained.

  The silica particles used in the present embodiment are preferably silica particles made of a hydrolyzate of an alkoxysilane oligomer. Conventional ordinary silica particles generally have a broad particle size distribution. For example, since they contain large particle diameters of 50 nm or more, transparency is often poor and the particles settle. There are also easy problems. Although what isolate | separated large particle size particle | grains (what is called a cut product) is also known, there exists a tendency which is easy to carry out secondary aggregation, and most things which transparency is impaired. In that respect, according to a specific synthesis method of hydrolysis of an oligomer of alkoxysilane, silica particles having a very small particle diameter can be stably obtained, and the silica particles have a property of being difficult to aggregate. There is an advantage that high transparency can be obtained.

  Here, the hydrolyzate refers to a product obtained by a reaction including at least a hydrolysis reaction, and may be accompanied by dehydration condensation and the like. Further, the hydrolysis reaction includes a dealcoholization reaction. Alkoxysilane is a compound in which an alkoxy group is bonded to a silicon atom, and these produce an alkoxysilane multimer (oligomer) by hydrolysis reaction and dehydration condensation reaction (or dealcoholization condensation). As will be described later, in order for the alkoxysilane oligomer to be compatible with water and a solvent, the alkyl chain of the alkoxysilane used in the present embodiment is preferably not too long, and usually has about 1 to 5 carbon atoms. Yes, preferably about 1 to 3 carbon atoms. Specific examples include tetramethoxysilane and tetraethoxysilane.

  Moreover, the reason for using alkoxysilane oligomer as a starting material without using alkoxysilane monomer (monomer) as a starting material is that the control of particle size is easy, the particle size distribution is narrow, and the particle size is easy to align. There are advantages. For this reason, it is easy to obtain a transparent composition, there is no problem of toxicity, and it is preferable for safety and health. The alkoxysilane oligomer can be produced by a known method (for example, the method described in JP-A-07-48454).

The hydrolysis reaction of the alkoxysilane oligomer is carried out by adding a certain amount of water to the alkoxysilane oligomer in a specific solvent and causing a catalyst to act. Silica ultrafine particles can be obtained by this hydrolysis reaction. As the solvent, one or more kinds of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers and the like can be used in combination, with alcohols and ketones being particularly preferred. .
Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octanol, n-propyl alcohol, acetylacetone alcohol and the like. Specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

In order to allow the hydrophilic silica particles to exist stably, it is preferable that the alkyl chains of alcohols and ketones used as a solvent are short. Particularly preferred are methanol, ethanol and acetone. Among these, acetone is preferable because it has a low boiling point and requires a relatively short time for the step of removing the solvent.
The amount of water necessary for the hydrolysis reaction of the alkoxysilane oligomer is usually 0.05 times or more, more preferably 0.3 times or more the lower limit of the number of moles of the alkoxy group possessed by the alkoxysilane oligomer. If the amount of water is too small, the silica particles do not grow to a sufficient size and the desired characteristics cannot be exhibited, which is not preferable. However, the amount of water is usually not more than 1 times the number of moles of alkoxy groups of the alkoxysilane oligomer. An excessively large amount of water is not preferable because the alkoxysilane oligomer easily forms a gel. The alkoxysilane oligomer is preferably compatible with the solvent and water used.

As a catalyst used for the hydrolysis reaction of an alkoxysilane oligomer, for example, one or more of metal chelate compounds, organic acids, metal alkoxides, boron compounds and the like can be used. In particular, metal chelate compounds and organic acids are preferred.
Specific examples of the metal chelate compound include, for example, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis Examples thereof include (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy) bis (acetylacetonate). One or more of these can be used in combination. In particular, aluminum tris (acetylacetonate) is preferably used.
Specific examples of the organic acid include formic acid, acetic acid, propionic acid, maleic acid and the like. Among these, one type or two or more types can be used in combination. In particular, maleic acid is preferably used. When maleic acid is used, there is an advantage that a cured product obtained by radiation curing has a good hue and tends to be less yellowish, which is preferable.
The amount of the catalyst component used for the hydrolysis reaction of the alkoxysilane oligomer is not particularly limited as long as the catalytic action is sufficiently exerted, but usually 0.1 part by weight with respect to 100 parts by weight of the alkoxysilane oligomer. Above, preferably 0.5 parts by weight or more. However, it is usually 10 parts by weight or less, preferably 5 parts by weight or less.

  In the present embodiment, by using silica particles composed of hydrolyzate of alkoxysilane oligomers, fine particles having a much larger particle diameter than conventional silica particles generally used as a filling component are used. There is an advantage that ultrafine particles can be blended in the radiation curable resin composition or the radiation cured product. In addition, silica particles made of hydrolyzate of alkoxysilane oligomers have the property of not easily agglomerating and have the advantage that they can be uniformly dispersed. For this reason, even if it mix | blends in a large quantity in a composition, the radiation transmittance is not impaired, and the dimensional stability and mechanical strength of a composition or hardened | cured material can be improved. Furthermore, as will be described later, the silica particles obtained by such a specific production method are subjected to a surface treatment with a silane coupling agent, and a larger amount of silica particles are agglomerated by blending them with a monomer and / or an oligomer thereof. It is possible to disperse without making it. Thus, the radiation cured product obtained from the radiation curable resin composition to which the present embodiment is applied has the advantage of having excellent properties that combine transparency and dimensional stability, mechanical strength, adhesion, and the like. is there.

In this Embodiment, other inorganic components other than the silica particle which consists of a hydrolyzate of the oligomer of an alkoxysilane can also be contained. Other inorganic components are not particularly limited, and for example, colorless metals or colorless metal oxides are used. Specific examples include silver, palladium, alumina, zirconia, aluminum hydroxide, titanium oxide, zinc oxide, calcium carbonate, clay mineral powder, and the like. Alumina, zinc oxide, or titanium oxide is preferable.
Although there is no particular limitation on the method for producing other inorganic components, a commercially available product is pulverized with a pulverizer such as a ball mill; a method such as sol-gel method is preferable because the particle size can be reduced. More preferably, it is produced by a sol-gel method. The other inorganic component is preferably ultrafine particles, and the lower limit of the number average particle diameter of the inorganic component is preferably 0.5 nm or more, more preferably 1 nm or more. When the number average particle size is excessively small, the cohesiveness of the ultrafine particles is extremely increased, and the transparency and mechanical strength of the cured product may be extremely decreased, or the characteristics due to the quantum effect may not be remarkable. The upper limit is preferably 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less, particularly preferably 15 nm or less, and most preferably 12 nm or less.

  Moreover, it is preferable that the particle size of other inorganic components is small. Specifically, the content of the other inorganic component having a particle size of preferably 30 nm or more, more preferably the content of the other inorganic component having a particle size of 15 nm or more is preferably 1% by weight with respect to the radiation curable resin composition. Hereinafter, it is more preferably 0.5% by weight or less. Or it is 1 volume% or less with respect to hardened | cured material, More preferably, it is 0.5 volume% or less. When the content of other inorganic components having a large particle size is large, light scattering increases, which is not preferable because the transmittance decreases.

  The content of the inorganic component in the radiation curable resin composition to which the present embodiment is applied is preferably included in a large amount within a range that can be contained in order to improve the dimensional stability and hardness characteristics of the cured product. Specifically, it is usually 5% by weight or more, preferably 10% by weight or more based on the radiation curable resin composition. Or it is 2 volume% or more normally with respect to a radiation curable resin composition, Preferably it is 5 volume% or more. However, it is preferably not too much to keep the transparency and mechanical strength of the cured product high, and is usually 60% by weight or less, preferably 40% by weight or less, more preferably based on the radiation curable resin composition. 30 wt% or less. Or it is 30 volume% or less normally with respect to a radiation curable resin composition, Preferably it is 20 volume% or less, More preferably, you may be 15 volume% or less. Among these, the content ratio of the silica particles in the inorganic component is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. However, the upper limit is 100% by weight.

(Silane coupling agent)
The silane coupling agent used in the present embodiment is a compound represented by the following formula (1).

(In formula (1), R is an alkyl group, R ′ is a group containing a reactive group, and Q ¹ and Q ² are each independently a monovalent organic group.)

As the alkyl group for R, C ₁ -C ₆ , more preferably C ₁ -C ₃ , and particularly preferably C ₁ and C ₂ alkyl groups are mentioned. The reactive group possessed by R ′ is preferably a radiation curable group such as an alkenyl group, a mercapto group, an oxylyl group, or an alkenylcarboxyoxy group, and an amino group, preferably a C ₆ or lower alkenyl group, amino group, A mercapto group, an oxylyl group, and an alkenylcarboxyoxy group having ₆ or less carbon atoms, more preferably a vinyl group, an amino group, a mercapto group, an oxylyl group, and a (meth) acryloyloxy group, still more preferably a vinyl group, a mercapto group. Group, oxylyl group, and (meth) acryloyloxy group. R ′ is a group having the above-mentioned reactive group, and the above-mentioned reactive group may be directly bonded to the Si atom, and is bonded to Si via a divalent linking group such as an alkylene group or an arylene group. You may do it.

Q ¹ and Q ² are preferably a group containing a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a reactive group. More preferably, it is an alkoxy group or a group containing a reactive group. When Q ¹ and Q ² are groups containing a reactive group, it is preferably the same group as R ′. The alkoxy group is preferably an alkoxy group represented by (RO—).
Preferable silane coupling agents include trialkoxysilane in which Q ¹ and Q ² are alkoxy groups, and more preferably trialkoxysilane in which three alkoxy groups are the same group. Mono and dialkoxysilanes may have low reactivity due to steric hindrance other than alkoxy groups. Specific examples of trialkoxysilane include, for example, epoxycyclohexylethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, Examples include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

  The silica particles used in this embodiment are surface-treated with a silane coupling agent. In the surface treatment, a Si—O—Si bond is generated through a dealcoholization reaction between the alkoxy group of the silane coupling agent and the hydroxy group on the surface of the silica particle. The amount of the silane coupling agent used for the surface treatment of the silica particles is usually 20 parts by weight or more, preferably 50% by weight or more, more preferably 100% by weight or more, still more preferably with respect to 100 parts by weight of the silica particles. Is 150% by weight or more. If the amount of the silane coupling agent used is too small, the surface of the silica particles is not sufficiently hydrophobized, which hinders uniform mixing with the monomer having a radiation curable group and / or its oligomer described later. There is a case. When the amount of the silane coupling agent used is excessively large, a large number of silane coupling components that do not bond to the silica particles are mixed in, and the transparency and mechanical properties of the resulting cured product are likely to be deteriorated. However, the amount of the silane coupling agent used is usually 400% by weight or less, preferably 350% by weight or less, and more preferably 300% by weight or less with respect to 100 parts by weight of the silica particles.

  The silane coupling agent may be partially hydrolyzed during the surface treatment of the silica particles. Accordingly, the composition after the surface treatment of the silica particles with the silane coupling agent includes a surface selected from a compound selected from the group consisting of a silane coupling agent, a hydrolysis product of the silane coupling agent, and a condensate thereof. Contains treated silica particles. In addition, there may be a condensate of silane coupling agents and / or a silane coupling agent and a hydrolysis product thereof. The hydrolysis product of the silane coupling agent refers to a product in which part or all of the alkoxysilane group contained in the silane coupling agent has undergone a hydrolysis reaction to become a hydroxysilane, that is, a silanol group. For example, when the silane coupling agent is epoxycyclohexylethyltrimethoxysilane, epoxycyclohexylethylhydroxydimethoxysilane, epoxycyclohexylethyldihydroxymethoxysilane, and epoxycyclohexylethyltrihydroxysilane are the examples. The silane coupling agents and / or the condensate of the silane coupling agent and its hydrolysis product are those in which an alkoxy group undergoes a dealcoholization reaction with a silanol group, or a Si-O-Si bond, or This refers to a silanol group that has undergone a dehydration reaction with another silanol group to form a Si—O—Si bond.

(Unreacted silane coupling agent)
In the radiation curable resin composition to which the present embodiment is applied, the amount ratio (A) of the unreacted silane coupling agent represented by the following formula is 6% or less, preferably 4%, more preferably 3% or less. It is. When the amount ratio (A) of the unreacted silane coupling agent is excessively large, gelation and white turbidity are likely to occur in the composition, and the storage stability of the composition is remarkably lowered.
In addition, a small amount ratio (A) of the unreacted silane coupling agent means that the amount of unreacted silane coupling agent per silica particle is small, and in this case, the silane cup necessary for coating the surface of the silica particle. The ring agent is sufficiently reacted, and aggregation / reaction of silica particles and the resulting white turbidity / gelation are prevented, and white turbidity and gelation due to the reaction between unreacted silane coupling agents are less likely to occur. Therefore, the smaller the ratio (A) of the unreacted silane coupling agent, the better.

In the present embodiment, the amount of the unreacted silane coupling agent in the radiation curable resin composition can be measured by a gas chromatography method. Specifically, peak separation and quantification can be easily performed by using a highly hydrophobic column filler and appropriately setting a temperature rising pattern using meta-xylene as an internal standard solution.
The specific amount of the unreacted silane coupling agent in the radiation curable resin composition is usually 0.1% by weight to 5% by weight, preferably 0.1% by weight to 1% by weight, more preferably 0.8%. 1% by weight to 0.8% by weight. When viewed in moles, ^{usually, 1.5 × 10 -3 mol / 100g~20} × 10 -3 mol / 100g, preferably ^{1.5 × 10 -3 mol / 100g~5 ×} 10 -3 mol / 100g, more preferably from ^{1.5 × 10 -3 mol / 100g~3 ×} 10 -3 mol / 100g. When the amount of the unreacted silane coupling agent is excessively large, the transparency or storage stability of the composition is remarkably deteriorated, which is not preferable.

On the other hand, as a method for quantifying the amount of silica particles in the radiation curable resin composition, first, the total amount of silicon atoms (Smol) is quantified by elemental analysis such as X-ray fluorescence, atomic absorption, IPC absorption, and molybdenum blue absorption. Next, the silicon atom ratio (pmol) derived from the silica particles in the total silicon atoms is determined by ²⁹ Si-NMR method. By these determinations, the amount of silicon in the silica particles in the composition (p × S (mol)) can be calculated. Next, from the amount of silicon in the silica particles in the composition, the weight of the silica particles in the composition (pS ÷ (atomic weight of silicon) × 60 (g) converted to SiO ₂ (= 60) can be obtained. .

  The specific amount of silica particles in the composition is usually 1% to 90% by weight, preferably 3% to 60% by weight, more preferably 5% to 50% by weight, and still more preferably 10% by weight. % To 40% by weight. If the amount of silica particles is too small, the surface hardness decreases, which is not preferable. If the amount of silica particles is excessively large, not only the transparency and storage stability are deteriorated, but also the adhesion to the substrate is lowered, which is not preferable.

(Monomer having radiation curable group and / or oligomer thereof)
Next, a monomer having a radiation curable group and / or an oligomer thereof will be described. A monomer having a radiation curable group and / or an oligomer thereof (hereinafter sometimes simply referred to as a monomer and / or an oligomer thereof) used in the radiation curable resin composition to which the present embodiment is applied is usually radiation. The curable resin composition contains 40% by weight or more, preferably 50% by weight or more. However, it is 95% by weight or less, preferably 90% by weight or less. When the content of the monomer and / or oligomer thereof is excessively small, the moldability and mechanical strength when forming the protective film are lowered, and cracks are likely to occur, which is not preferable. When the content of the monomer and / or oligomer thereof is excessively large, the surface hardness of the cured product is lowered, which is not preferable.

  The radiation curable group possessed by the monomer and / or oligomer thereof is not particularly limited as long as it is a functional group having polymerizability by radiation, and usually a photocation reaction such as a radical reactive group or a photocation curable glycidyl group. Groups having photonic properties, groups having photoanion reactivity, groups having photothiol / ene reactivity such as thiol groups, and the like. Of these, a group having radical reactivity is preferable.

  Examples of the functional group having radical reactivity include a (meth) acryloyl group and a vinyl group. Of these, a (meth) acryloyl group is particularly preferable from the viewpoints of polymerization reaction rate, transparency, and coatability. When a (meth) acryloyl group is used, 50% or more of the total number of radiation curable groups possessed by the monomer and / or oligomer thereof may be a (meth) acryloyl group. However, the expression “(meth) acrylate” here means either acrylate or methacrylate. In particular, it is preferable to mainly use a compound having two or more radiation curable groups in one molecule of the monomer and / or oligomer thereof. Here, “mainly” means to occupy 50% by weight or more of all components of the monomer and / or oligomer thereof. In this case, a three-dimensional network structure can be formed by a polymerization reaction by radiation, and an insoluble and infusible cured resin can be obtained.

  In the present embodiment, the radiation curable functional group is polymerized with radiation such as active energy rays (for example, ultraviolet rays), electron beams, etc. to cure at a high speed while the ultrafine particles are highly dispersed. Can do. Radiation curing generally proceeds at a very high rate in seconds. Therefore, it is possible to prevent an undesirable phenomenon such that the ultrafine particles move or aggregate in the curing process, and thus a cured resin having a high degree of transparency can be obtained. On the other hand, thermal polymerization takes several tens of minutes to several hours, which is not preferable because the ultrafine particles may move and aggregate during polymerization and become cloudy.

  In the present embodiment, only the monomer may be used, only the oligomer may be used, or both may be mixed and used. Many of the monomers are liquids having a low viscosity as compared with the oligomers, which is advantageous when mixed with other components. Moreover, there exists an advantage which is easy to shape | mold, such as coating and cast molding. However, some of them are toxic and need attention. On the other hand, oligomers are generally high in viscosity and may be difficult to handle. However, there are advantages that the degree of surface curing is excellent, the curing shrinkage tends to be small, and the cured product has many excellent mechanical properties, particularly tensile properties and bending properties.

  The monomer or oligomer may be hydrophilic, but is preferably hydrophobic. As the monomer and / or its oligomer, it is preferable to use an oligomer having a relatively high molecular weight. The molecular weight is preferably 1000 or more, more preferably 2000 or more. The upper limit of the molecular weight of the oligomer is not particularly limited, but is usually 50000 or less, preferably 30000 or less, more preferably 20000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. By using such a relatively high molecular weight oligomer, the degree of surface curing and adhesion of the cured product tend to be improved. The reason for this is not clear, but the composition containing the oligomer tends to reduce the curing shrinkage, so that the functional group density is relatively small and the curing reaction is performed efficiently, and the residual at the adhesion interface due to the curing shrinkage. It is estimated that the small distortion is related to the degree of surface hardening and the improvement of adhesion. In addition, such high molecular weight oligomers may be used alone or in combination of two or more. Moreover, you may use together with other monomer and oligomer of lower molecular weight.

  When oligomers with extremely high molecular weight are used, the viscosity of the composition may increase, and moldability and workability may deteriorate.In this case, the amount of low molecular weight oligomers and monomers and reactive diluent added may be reduced. It can be improved by increasing it. Although it does not specifically limit as a monomer and / or its oligomer, What has the group which can form an intramolecular hydrogen bond and an intermolecular hydrogen bond in a molecule | numerator is preferable. The monomer and / or oligomer thereof having a group capable of forming an intramolecular hydrogen bond or intermolecular hydrogen bond has a group containing a hydrogen atom that is easily released in the monomer and / or oligomer molecule, and Monomers and / or oligomers thereof capable of forming an intramolecular or intermolecular hydrogen bond.

  Examples of the group containing a hydrogen atom that is easily released include a hydroxyl group, formyl group, carboxyl group, mercapto group, thioformyl group, thiocarboxyl group, sulfyl group, sulfo group, sulfamoyl group, sulfoamino group, amino group, imino group, and carbamoyl group. And an amide group. More preferred are a hydroxyl group and an amide group. The intramolecular or intermolecular hydrogen bond generated by these groups enhances the cohesiveness of organic molecules, inhibits free movement of oxygen in the composition, inhibits radical polymerization inhibition, and improves the degree of surface hardening.

The monomer and / or oligomer thereof is more preferably a monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof. Particularly preferred are a monomer having a urethane bond and / or an oligomer thereof.
When the monomer and / or oligomer thereof is a condensed alicyclic acrylate monomer and / or oligomer thereof, the condensed alicyclic acrylate monomer and / or oligomer and a monomer having a urethane bond or a hydroxyalkylene group and / or Or it is preferable to mix and use the oligomer. The condensed alicyclic acrylate includes a compound containing a condensed aliphatic cyclic hydrocarbon group and an acryloyl group.

Specifically, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate, and mixtures thereof Bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = diacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = dimethacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = acrylate methacrylate and condensed alicyclic diacrylate monomers such as mixtures thereof and / or oligomers thereof.

(Monomer having urethane bond or hydroxyalkylene group and / or oligomer thereof)
When the monomer and / or oligomer having a urethane bond or a hydroxyalkylene group is used as the monomer and / or oligomer used in the present embodiment, there is an advantage that the adhesion and surface curing degree of the obtained resin cured product are increased. is there. The phenomenon that adhesion improves when a monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof is used is that the interaction with the adherend is strengthened by the electrical polarity of the urethane bond or hydroxyalkylene group. It is thought to originate from. In addition, it is not clear why the surface curing degree is improved when a monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof is used, but the monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof are fixed. In the composition containing more than the amount, since the intramolecular hydrogen bond and intermolecular hydrogen bond derived from the electrical polarity of the urethane bond or hydroxyalkylene group are easily formed, the cohesion of the organic molecule is enhanced, and as a result It is presumed that the main reason is that free movement of oxygen in the composition is inhibited, and inhibition of radical polymerization is suppressed.
Moreover, it is preferable that the monomer which has a urethane bond or a hydroxyalkylene group, and / or its oligomer itself also have a radiation-curable group. As a result, the monomer or oligomer having a urethane bond or a hydroxyalkylene group is incorporated into the radiation-cured network structure to be integrated, so that the cohesiveness is increased, and as a result, cohesive failure hardly occurs and the adhesiveness is improved. Moreover, since the effect of restricting the free movement of oxygen is enhanced, there is an advantage that the degree of surface hardening is improved.

  As a method for producing a monomer having a urethane bond, a method of reacting a chloroformate with ammonia or an amine, a method of reacting an isocyanate with a hydroxyl group-containing compound, a method of reacting urea with a hydroxyl group-containing compound, etc. are known. The method may be carried out according to the above method, and when the monomer has a reactive group, it can be oligomerized. Of these, it is generally easy to use a urethane oligomer, and the urethane oligomer is usually an addition reaction between a compound having two or more isocyanate groups in the molecule and a compound containing a hydroxyl group by a conventional method. Manufactured.

  Examples of compounds having two or more isocyanate groups in the molecule include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone. Examples thereof include polyisocyanates such as diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate. Of these, one or more of bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate are used in combination because of the favorable hue of the resulting composition. Is preferred.

  As the compound containing a hydroxyl group, polyols containing two or more hydroxyl groups are preferably used. Specific examples thereof include alkyl polyols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, sorbitol, mannitol, and glycerin, and polyether polyols that are multimers thereof, and these polyols. And polyester polyols such as polyester polyols synthesized from polyhydric alcohols and polybasic acids, and polycaprolactone polyols.

  It is preferable that the urethane oligomer obtained by these contains a polyether polyol as a compound containing a hydroxyl group, and the average content of structural units derived from the polyether polyol in one molecule of the urethane oligomer is 20% by weight. % Or more, more preferably 25% by weight or more, and particularly preferably 30% by weight or more. The upper limit is not particularly limited, but is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less. When the content ratio of the polyether polyol is excessively small, the cured product becomes brittle, and the elastic modulus is too high to easily generate internal stress, which tends to cause deformation. On the other hand, if it is excessively large, the surface hardness of the cured product is lowered, and problems such as easy scratching tend to occur.

  The addition reaction of an isocyanate compound and a hydroxyl compound is carried out by a known method, for example, in the presence of an isocyanate compound, a mixture of a hydroxyl compound and an addition reaction catalyst, for example, dibutyltin laurate is added dropwise at 50 ° C to 90 ° C. This can be done. In particular, when synthesizing a urethane acrylate oligomer, it can be produced by using a part of a compound containing a hydroxyl group as a compound having both a hydroxyl group and a (meth) acryloyl group. The amount used is usually 30 to 70% of the total hydroxyl group-containing compound, and the molecular weight of the resulting oligomer can be controlled according to the proportion. Examples of compounds having both a hydroxyl group and a (meth) acryloyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, an addition reaction product of a glycidyl ether compound and (meth) acrylic acid, Examples include mono (meth) acrylates of glycol compounds.

  Urethane oligomer having (meth) acryloyl groups at both ends by addition reaction of one compound having two or more isocyanate groups in the molecule and two compounds having both a hydroxyl group and a (meth) acryloyl group Can be manufactured. In particular, urethane oligomers having (meth) acryloyl groups at both ends have the advantage that the adhesion and surface curing degree of the resulting cured resin are further increased.

  The monomer having a urethane bond and / or the oligomer thereof preferably further has an acidic group in the molecule. Here, the acidic group means a functional group having acidity, and examples of the acidic group include a sulfonic acid group, a phosphoric acid group, a carboxyl group, and a tertiary amine compound neutralized salt or metal salt thereof. Can be mentioned. In this case, compounds having these acidic groups may be used as the compounds used in the method for producing the above-mentioned monomer having a urethane bond and / or oligomer thereof, and hydroxyl groups having acidic groups are particularly used during oligomer production. It is preferable to use a group-containing compound.

  As the compound containing a hydroxyl group having an acidic group, polyols containing two or more hydroxyl groups are preferable. Specific examples of polyols having an acidic group include alkali metal salts such as 2-sulfo-1,4-butanediol and its sodium salt, 5-sulfo-di-β-hydroxyethyl isophthalate and its sodium salt. Alkali metal salts such as N, N-bis (2-hydroxyethyl) aminoethylsulfonic acid and its tetramethylammonium salt, its tetraethylammonium salt and its benzyltriethylammonium salt, and their alkali metal salts and amines Salts: Phosphate esters such as bis (2-hydroxyethyl) phosphate and its tetramethylammonium salt, alkali metal salts such as its sodium salt, and amine salts and alkali metal salts thereof; dimethylolacetic acid, dimethylolpropionic acid, dimethylol Butanoic acid Alkanol carboxylic acids such as dimethylol heptanoic acid, dimethylol nonanoic acid, dihydroxybenzoic acid, and their caprolactone adducts; in one molecule such as a half ester compound of polyoxypropylene triol and maleic anhydride or phthalic anhydride Examples include compounds having two hydroxyl groups and a carboxyl group, and among them, compounds having a carboxyl group as an acidic group are preferred.

  In addition, as a method of introducing an acidic group into a monomer having a urethane bond and / or an oligomer thereof, an isocyanate group-containing compound having an acidic group as described above is used and / or a hydroxyl group having an acidic group is contained. The method of using a compound etc. is mentioned. Furthermore, by reacting a monomer having a urethane bond and / or an oligomer thereof with a compound having at least one functional group other than a hydroxyl group having reactivity with an isocyanate group, for example, an amino group and having an acidic group, A method of introducing an acidic group into a monomer having a urethane bond and / or an oligomer thereof may also be employed. Specific examples of the compound in that case include 1-carboxy-1,5-pentyldiamine, 3,5-diaminobenzoic acid, and the like.

The content of acidic groups in the monomer having an acidic group-containing urethane bond and / or its oligomer is 0.5 × 10 ⁻⁴ eq / g or more with respect to the monomer having a urethane bond and / or its oligomer. It is preferable that it is 1.5 × 10 ⁻⁴ eq / g or more. Further, it is preferably 30 × 10 ⁻⁴ eq / g or less, more preferably 8 × 10 ⁻⁴ eq / g or less.
When a monomer having an acidic group-containing urethane bond and / or an oligomer thereof is used, the amount of acidic groups derived from the monomer and / or oligomer having a radiation curable group in the entire composition is 0.1 × 10 ^−4. The amount used is preferably adjusted to be eq / g or more, more preferably 1 × 10 ⁻⁴ eq / g or more, and particularly preferably 1.5 × 10 ⁻⁴ eq / g or more. . Further, it is preferably 13 × 10 ⁻⁴ eq / g or less, more preferably 10 × 10 ⁻⁴ eq / g or less, and particularly preferably 4 × 10 ⁻⁴ eq / g or less. When the content of the acidic group is excessively small, the effect of improving the interlayer adhesion as a cured product is insufficient, and not only does the peeling easily occur, but the cured product combined with silica particles described later tends to be brittle. . When the content of the acidic group is excessively large, the flexibility as a cured product is lowered, and rather the interlayer adhesion tends to be lowered.

The monomer having a hydroxyalkylene group mainly means so-called epoxy (meth) acrylate. Epoxy (meth) acrylate is produced by reacting an epoxy compound having at least one epoxy group in one molecule with an unsaturated monobasic acid in the presence of a specific esterification catalyst and a polymerization inhibitor. be able to.
As an epoxy compound, an epoxy compound obtained by a reaction between a bisphenol A and / or F compound and epichlorohydrin having an epoxy equivalent of 170 to 2000, preferably an epoxy equivalent of 170 to 1000 having a low viscosity can be used. In addition, epoxy compounds obtained by reaction of brominated bisphenol A compounds with epichlorohydrin, epoxy compounds obtained by reaction of hydrogenated bisphenol A with epichlorohydrin, further phenol novolac type epoxy compounds, cresol novolak type A novolak type epoxy compound such as an epoxy compound can also be used. These epoxy compounds can be used alone or in admixture of two or more. Among these, bisphenol A and / or F type epoxy compounds are preferable because they are excellent in fluidity, impact resistance, and boiling resistance, and have good adhesion to the adherend.
The unsaturated monobasic acid to be reacted with the epoxy compound is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. These acids can be used alone or in combination of two or more.
The compounding ratio of the epoxy compound and the unsaturated monobasic acid is usually in a range where the carboxyl group in the unsaturated monobasic acid is 0.9 equivalent to 1.2 equivalent relative to the epoxy group in the epoxy compound. Of these, a range of 1 ± 0.05 equivalent is preferable in that a resin having excellent curability and storage stability can be obtained. When the blending ratio is smaller than this range, the residual amount of the epoxy group is increased, so that a side reaction product of the epoxy group and the secondary hydroxyl group in the epoxy acrylate is generated, and the storage property is greatly reduced. When the blending ratio is larger than this range, the unsaturated monobasic acid remaining after the reaction is not preferable because the curing time becomes extremely long.

  The monomer having a hydroxyalkylene group and / or an oligomer thereof preferably further has an acidic group in the molecule. Examples of the acidic group include those described in the description of the acidic group contained in the above-described monomer having a urethane bond and / or oligomer thereof. The method for introducing an acidic group into the molecule of a monomer having a hydroxyalkylene group and / or an oligomer thereof is not particularly limited as long as a known method is used. For example, a method for introducing a carboxyl group includes a method in which a cyclic acid anhydride is reacted with a hydroxyl group. The acid anhydride in this case is not particularly limited. For example, maleic anhydride, succinic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, naphthalene-1,8: 4,5-tetracarboxylic acid Acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid = 3,4-anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride An acid or the like can be used. Of these, maleic anhydride and succinic anhydride are particularly preferable in terms of excellent transparency and light resistance. A method of reacting a cyclic acid anhydride with a hydroxyl group of a monomer or oligomer having a hydroxyalkylene group is a method of stirring for several hours at a temperature in the range of room temperature to 150 ° C., more preferably 40 ° C. to 100 ° C. after mixing. Etc.

The monomer and / or oligomer thereof used in the present embodiment is preferably a highly transparent material, for example, a compound having no aromatic ring. Resin compositions and cured products using aromatic ring-containing monomers and / or oligomers thereof are colored, or even if they are not initially colored, they are colored during storage or become more colored. There is so-called yellowing. It is thought that this is because the double bond part forming the aromatic ring irreversibly changes its structure by energy rays.
For this reason, the monomer and / or oligomer thereof has a structure that does not have an aromatic ring, so that there is no deterioration in hue and light transmittance does not decrease, and applications such as optoelectronics that are colorless and transparent are required. There are advantages that make it particularly suitable for applications.

In the monomer having urethane bond and / or its oligomer, the monomer having no aromatic ring and / or the oligomer thereof are the isocyanate group-containing compound not containing aromatic ring and the hydroxyl group-containing compound not containing aromatic ring in the above-mentioned production method. Can be produced by addition reaction. For example, as the isocyanate compound, it is preferable to use one or more of bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate in combination.
In the production method described above, a monomer having a hydroxyalkylene group and / or an oligomer thereof having no aromatic ring and / or an oligomer thereof are an epoxy compound having no aromatic ring and an unsaturated-basic acid having no aromatic ring. Can be made to react. Examples of the epoxy compound having no aromatic ring include a hydrogenated bisphenol A type epoxy compound, a hydrogenated bisphenol F type epoxy compound, or an epoxy not having an aromatic ring such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. It is preferable to use an epoxy compound obtained by reacting the compound with epichlorohydrin.

(Other monomers and / or oligomers thereof)
When a monomer having a urethane bond or a hydroxyalkylene group and / or oligomer thereof is used as the monomer and / or oligomer thereof, other radiation curable monomer and / or oligomer thereof, preferably bifunctional or trifunctional (meta ) An acrylate compound may be mixed. The amount of the other radiation-curable monomer and / or oligomer thereof used is preferably 50% by weight or less, more preferably 30% by weight or less, with respect to the composition other than the silane-treated silica particles.

Examples of the bifunctional or trifunctional (meth) acrylate compound include alicyclic poly (meth) acrylate, alicyclic poly (meth) acrylate, and aromatic poly (meth) acrylate. Specifically, triethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] propane, bis (hydroxymethyl) tricyclo [5.2.1.0 ² , ⁶ ] decane = dimethacrylate, p-bis [β- (meth) acryloyloxyethylthio] xylylene, Divalent (meth) acrylates such as 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenylsulfone, trimethylolpropane tris (meth) acrylate, glycerin tris (meth) acrylate, pentaerythritol tris ( Trivalent (meth) acrylates such as (meth) acrylate Tetravalent (meth) acrylates such as pentaerythritol tetrakis (meth) acrylate, indeterminate polyvalent (meth) acrylates such as epoxy acrylate and the like. Of these, divalent (meth) acrylates are preferably used because of the controllability of the cross-linking reaction.

  Trifunctional or higher functional (meth) acrylates are preferably added for the purpose of improving the heat resistance of the crosslinked structure of the cured product and improving the surface hardness. Specific examples thereof include trifunctional (meth) acrylates having an isocyanurate skeleton in addition to the above-described trimethylolpropane tris (meth) acrylate and the like. Furthermore, a hydroxyl group-containing (meth) acrylate compound is preferably added for the purpose of improving adhesiveness and adhesion. Specific examples of the compound include hydroxyethyl (meth) acrylate.

  Among the (meth) acrylates described above, it is particularly preferable to add the following component A and the following component B in view of achieving a good balance between transparency and low optical distortion of the resulting polymer. Component A is a bis (meth) acrylate having an alicyclic skeleton represented by the following general formula (2).

In General Formula (2), R ^a and R ^b are each independently a hydrogen atom or a methyl group, R ^c and R ^d are each independently an alkylene group having 6 or less carbon atoms, x Is 1 or 2, and y is 0 or 1.
Specific examples of the component A represented by the general formula (2) include bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxymethyl) tricyclo [5.2. 1.0 ^2,6] decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6] decane = acrylate methacrylate and mixtures thereof, bis (hydroxymethyl) pentacyclo [6.5. 1.1 ^{3, 6} . 0 ^2,7 . 0 ^9,13 ] pentadecane = diacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = dimethacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = acrylate methacrylate and mixtures thereof. These tricyclodecane compounds and pentacyclodecane compounds may be used in combination.

  Component B is a bis (meth) acrylate having a sulfur atom represented by the following general formula (3).

In General Formula (3), R ^a and R ^b are each independently a hydrogen atom or a methyl group, R ^e is an alkylene group having 1 to 6 carbon atoms, and Ar is a carbon number. It is an arylene group or an aralkylene group which is 6 to 30, and these hydrogen atoms may be substituted with a halogen atom other than a fluorine atom. X is an oxygen atom or a sulfur atom, respectively. When X is an oxygen atom, at least one of Y is a sulfur atom or a sulfone group (—SO ₂ —), and at least one of X is a sulfur atom. Y represents a sulfur atom, a sulfone group, a carbonyl group (—CO—), and an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylenethioether group, and an aralkylene, each having 1 to 12 carbon atoms. It is a thioether group, j and p are each independently an integer of 1 to 5, k is an integer of 0 to 10, and when k is 0, X is a sulfur atom.

Specific examples of the component B represented by the general formula (3) include, for example, α, α′-bis [β- (meth) acryloyloxyethylthio] -p-xylene, α, α′-bis [β- ( (Meth) acryloyloxyethylthio] -m-xylene, α, α′-bis [β- (meth) acryloyloxyethylthio] -2,3,5,6-tetrachloro-p-xylene, 4,4′- Bis [β- (meth) acryloyloxyethoxy] diphenyl sulfide, 4,4′-bis [β- (meth) acryloyloxyethoxy] diphenylsulfone, 4,4′-bis [β- (meth) acryloyloxyethylthio] Diphenyl sulfide, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl sulfone, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl 2,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl ketone, 5,5′-tetrabromodiphenyl ketone, β, β′-bis [p- (meth) acryloyloxyphenylthio] diethyl And ether, β, β′-bis [p- (meth) acryloyloxyphenylthio] diethylthioether, and the like. These may use multiple types together.
Among these components, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate has excellent transparency and heat resistance, and is particularly preferably used.

(Reactive diluent)
A reactive diluent may be added to the radiation curable resin composition to which this embodiment is applied for the purpose of adjusting the viscosity of the composition. The usage-amount of a reactive diluent is 0.5 to 80 weight% with respect to compositions other than an inorganic component, Preferably it is 1 to 50 weight%. If the amount of the reactive diluent used is excessively small, the dilution effect is small, and if it is excessively large, it tends to be brittle and tends to decrease the mechanical strength, and the curing shrinkage increases, which is not preferable. Here, the reactive diluent is a low-viscosity liquid compound and is usually a monofunctional low-molecular compound. Examples thereof include compounds having a vinyl group or (meth) acryloyl group, mercaptans, and the like.

The reactive diluent is preferably radiation curable and includes, for example, a compound having a vinyl group or a (meth) acryloyl group. Specific examples of such compounds include aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, (meth) acrylamides, (meth) acrylic esters, and di (meth) acrylates. . Of these, compounds having a structure having no aromatic ring are preferred from the viewpoint of hue and light transmittance. Specifically, it has an alicyclic skeleton such as (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylate having a tricyclodecane skeleton ( (Meth) acrylates, (meth) acrylamides such as N, N-dimethylacrylamide, aliphatic (meth) acrylates such as hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. have good hue and viscosity In particular, it is preferably used.
In addition, compounds having both a hydroxyl group and a (meth) acryloyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate can also be used. The adhesiveness of the composition to glass may be improved, which is preferable.

(Polymerization initiator)
It is preferable to add a polymerization initiator that initiates a polymerization reaction by active energy rays (for example, ultraviolet rays) to the radiation curable resin composition to which the present embodiment is applied. As such a polymerization initiator, a radical generator which is a compound having a property of generating radicals by light is generally used, and known compounds can be used. Specific examples of the radical generator include, for example, benzophenone, benzoin methyl ether, benzoin isopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl. Examples thereof include diphenylphosphine oxide, and a plurality of these may be used in combination. Of these, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone are preferred.

  The addition amount of the polymerization initiator is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, more preferably 0.001 part by weight or more with respect to 100 parts by weight of the total of the monomer and / or oligomer containing the radiation curable group. 05 parts by weight or more. However, it is usually 10 parts by weight or less, preferably 8 parts by weight or less. If the amount added is too large, the polymerization reaction may proceed rapidly and not only increase the optical distortion but also deteriorate the hue. If the amount is too small, the composition may not be sufficiently cured. . In addition, when starting a polymerization reaction with an electron beam, although the polymerization initiator mentioned above can also be used, it is preferable not to use a polymerization initiator.

  In the radiation curable resin composition to which the present embodiment is applied, a surface tension adjusting agent is usually used for the purpose of reducing the surface tension of the composition and improving the coating property to the substrate. Specific examples of the surface tension adjusting agent include, for example, low molecular and high molecular surfactants, silicone compounds and various modified products thereof (polyether modified, fluorine modified, etc.), sorbitan esters, other various leveling agents, antifoaming agents, Examples include rheology control agents and mold release agents. Of these, silicone compounds such as Polyflow KL510 (manufactured by Kyoeisha Chemical Co., Ltd.) are preferred, and polyether-modified silicone compounds such as KF351A (manufactured by Shin-Etsu Chemical Co., Ltd.) and fluorine-modified surfactants preferably reduce surface tension. It is preferable because it exhibits not only the property of preventing coating defects but also antifouling property, slipperiness and environmental resistance. The addition amount of the surface tension adjusting agent is usually 5% by weight or less, preferably 3% or less, more preferably 0.01% by weight to 1% by weight with respect to the composition, although it depends on the type.

(solvent)
In the radiation curable resin composition to which this embodiment is applied, a solvent may be usually used. The solvent is preferably colorless and transparent, and specifically, one or a combination of two or more of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers and the like can be used. . Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octanol, n-propyl alcohol, acetylacetone alcohol, and the like. Specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Among these, methanol, ethanol, or acetone is particularly preferable. The amount of the solvent used is preferably 95% or less, more preferably 30% or less, more preferably 20% or less, particularly preferably 10% or less, particularly preferably 5% or less, most preferably based on the composition. Is solvent-free.

(Auxiliary ingredient)
You may add auxiliary components, such as an additive, to the radiation curable resin composition to which this Embodiment is applied as needed. As auxiliary components, for example, stabilizers such as antioxidants, heat stabilizers, or light absorbers; fillers such as glass fibers, glass beads, mica, talc, kaolin, metal fibers, metal powders; carbon fibers, carbon black, graphite, carbon materials such as fullerene and carbon nanotubes, C ₆₀ (fillers are generically fullerenes like referred to inorganic filler component.); antistatic agents, plasticizers, mold release agents, defoaming Modifiers such as additives, leveling agents, anti-settling agents, surfactants, thixotropy imparting agents; colorants such as pigments, dyes, hue control agents; curing necessary for the synthesis of monomers and / or oligomers thereof or inorganic components Examples thereof include agents, catalysts, and curing accelerators. The addition amount of these auxiliary components is usually 20% by weight or less of the radiation curable resin composition or the radiation cured product.

In addition, the radiation curable resin composition to which the present embodiment is applied includes monomers other than radiation curable and / or for the purpose of improving mechanical properties and heat resistance, and balancing various properties. Or you may further mix the oligomer. Although the kind of monomer and / or its oligomer is not specifically limited, Specifically, a thermoplastic resin, a thermosetting resin monomer, and / or its oligomer are used.
Examples of the thermoplastic resin include polystyrene; polymethyl methacrylate; polyarylate, polyester such as O-PET (manufactured by Kanebo); polycarbonate; polyethersulfone; ZEONEX (manufactured by ZEON Corporation), and fats such as ARTON (manufactured by JSR Corporation). Cyclic thermoplastic resins; cyclic polyolefins such as Apel (manufactured by Mitsui Chemicals) and the like can be mentioned, and polycarbonate or polyethersulfone is preferred from the viewpoint of transparency and dimensional stability. The thermoplastic resin is preferably 20% by weight or less based on the composition other than the inorganic component.
As the thermosetting resin monomer and / or oligomer thereof, an epoxy resin; Rigolite (manufactured by Showa Denko) or the like is used, and a high purity epoxy resin is preferable from the viewpoint of transparency and dimensional stability. The thermosetting resin is preferably 50% by weight or less based on the composition other than the inorganic component.

  The viscosity at 25 ° C. of the radiation curable resin composition to which the present embodiment is applied is usually preferably 10 centipoises or more, 100 centipoises or more, 1000 centipoises or more, and more preferably 2000 poises or more. Also, it is usually 100,000 centipoises or less, 10,000 centipoises or less, and preferably 5,000 centipoises or less. If the viscosity at 25 ° C. is excessively low, it is difficult to form a protective film having a thickness of 50 μm or more. Therefore, it cannot be used for an information recording medium that requires such a thick protective film. Absent. An excessively high viscosity is not preferable because it is difficult to form a protective film having a smooth surface. The viscosity at 25 ° C. of the radiation curable resin composition may be measured with an E-type viscometer, a B-type viscometer or a vibration-type viscometer. Methods for adjusting the viscosity include techniques such as addition of diluent, solvent removal, molecular weight control of radiation curable oligomer, addition of thickener or rheology control agent, preferably addition of diluent, radiation The molecular weight control of the curable oligomer and the addition of a thickener are used, more preferably the addition of a diluent.

  The transparency of the radiation curable resin composition is not particularly limited as long as the cured product obtained by curing the composition is transparent depending on the application, and the transparency of the composition itself is not particularly limited, but preferably at 550 nm The light transmittance with an optical path length of 0.1 mm is 80% or more, more preferably 85% or more. More preferably, the light transmittance at an optical path length of 0.1 mm at 400 nm is 80% or more, more preferably 85% or more. When the light transmittance is excessively low, transparency during curing tends to be greatly impaired, and when a cured product is used for an optical recording medium, a reading error increases when reading recorded information, which is not preferable.

  The radiation curable resin composition has a surface tension at 25 ° C. of 50 mN / m or less, 40 mN / m or less, preferably 35 mN / m or less, more preferably 30 mN / m or less. If the surface tension is too high, the spreadability of the composition at the time of coating deteriorates, and not only the amount of the composition required at the time of coating increases, but also a defect is caused, which is not preferable. The smaller the surface tension, the better, but it is usually 10 mN / m or more. The surface tension may be measured using a surface tension meter (for example, CBVP-A3 type manufactured by Kyowa Interface Science Co., Ltd.). As a method for adjusting the surface tension, addition of a surface tension adjusting agent can be mentioned.

It is preferable that the radiation curable resin composition to which this exemplary embodiment is applied does not substantially contain a solvent. Here, “substantially containing no solvent” means a state in which the content of a so-called organic solvent having volatility or a low boiling point is very low, and the solvent content in the composition is usually 1% or less. It is preferably 0.1% or less, more preferably 0.01% or less. For simplicity, it means a state in which no odor of the organic solvent is observed. As another method, a radiation curable resin composition is spin-coated at a thickness of 100 ± 15 microns, heated at 70 ° C. for 1 minute, and then irradiated with ³ J / cm ² of ultraviolet rays or 5 Mrads of electron beams, or Then, after curing until the degree of surface curing described later becomes ◯, bubbles or white turbidity due to volatilization of the solvent remaining in the cured product does not occur.

(Method for producing radiation curable resin composition)
Next, the manufacturing method of the radiation curable resin composition to which this Embodiment is applied is demonstrated.
The radiation curable resin composition to which the present embodiment is applied is particularly a method in which the silane-treated silica particle component surface-treated with a silane coupling agent is uniformly dispersed and mixed in the monomer and / or oligomer thereof. There is no limitation. Specifically, (1) a method in which a silane-treated silica particle powder is prepared and then directly dispersed in a monomer and / or its oligomer in an appropriate liquid state, (2) a monomer and / or its in an appropriate liquid state A method of preparing silane-treated silica particles in an oligomer; (3) a method of dissolving silane-treated silica particles in a liquid medium and then dissolving the monomer and / or its oligomer and then removing the solvent; and (4) a solvent. A method of removing the solvent after preparing the silane-treated silica particles in a solution in which the monomer and / or oligomer thereof is dissolved, (5) After preparing the silane-treated silica particles and monomer and / or the oligomer thereof in the solvent And a method for removing the solvent. Of these, the method (3) is most preferable because it is easy to obtain a product having high transparency and good storage stability.

  In the method (3), specifically, (a) in a liquid medium such as a solvent, a surface treating agent or a diluent, an alkoxysilane oligomer is hydrolyzed at a temperature of 10 ° C. to 100 ° C. to produce silica particles. A step of synthesizing, (b) a step of reacting the synthesized silica particles with a silane coupling agent to prepare silane-treated silica particles, and (c) mixing the prepared silane-treated silica particles with a monomer and / or an oligomer thereof. It is preferable to sequentially perform the step and (d) the step of removing the solvent at a temperature of 10 ° C to 75 ° C. According to this production method, it is possible to more easily obtain a radiation curable resin composition in which silane-treated silica particles having ultrafine particles and a uniform particle size are highly dispersed.

First, in the step (a), an alkoxysilane oligomer, a catalyst and water are added in a liquid medium to hydrolyze the alkoxysilane oligomer to synthesize silica particles. The liquid medium is not particularly limited, but is preferably compatible with the monomer and / or its oligomer. Specifically, a solvent, a surface treatment agent or a diluent is used. The surface treatment agent and diluent are the same as described above. As the solvent, preferably used are alcohols or ketones, particularly preferably an alcohol of C ₁ -C _4, acetone, methyl ethyl ketone or methyl isobutyl ketone is used. The amount of the liquid medium is preferably 0.3 to 10 times that of the alkoxysilane oligomer.
Examples of the catalyst include organic acids such as formic acid and maleic acid; inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid; and hydrolytic catalysts such as metal complex compounds such as acetylacetone aluminum, dibutyltin dilaurate and diztiltin dioctate. . The amount of the catalyst used is preferably 0.1 to 3% by weight based on the oligomer of alkoxysilane. The amount of water is preferably 10 to 50% by weight based on the oligomer of alkoxysilane. The hydrolysis temperature ranges from 10 ° C to 100 ° C. An excessively low hydrolysis temperature is not preferable because the reaction for forming silica particles does not proceed sufficiently. An excessively high hydrolysis temperature is not preferable because the gelation reaction of the oligomer tends to occur. The hydrolysis time is preferably 30 minutes to 1 week.

  Next, in the step (b), the silica particles are surface-treated with a silane coupling agent. In order to obtain a composition in which the amount ratio (A) of the unreacted silane coupling agent in the radiation curable resin composition to which the present embodiment is applied is 6% or less, the silica particles are surfaced with the silane coupling agent. In the treatment, it is preferable to carry out the reaction under the following conditions. That is, the surface treatment reaction of the silica particles with the silane coupling agent usually proceeds at room temperature (25 ° C.), more preferably 60 ° C. or more, still more preferably 70 ° C. or more, particularly preferably 75 ° C. or more. The reaction is preferably performed at a temperature of 80 ° C. or higher. By performing the surface treatment reaction at 60 ° C. or higher, the transparency and storage stability of the composition are dramatically improved. The time required for the reaction is usually 0.5 to 24 hours. During the reaction, the stirring is performed to advance the reaction. The reaction time is appropriately adjusted depending on the reaction temperature. The reaction time depends on the type of silane coupling agent used, but in general, when the reaction temperature is 60 ° C, it is 8 hours or more, when it is 65 ° C, it is 5 hours or more, and when it is 70 ° C, it is 2 hours or more. In the case of 75 ° C., the reaction is preferably performed for 0.5 hour or longer. However, if the reaction temperature is higher than 90 ° C., white turbidity or gelation tends to occur, which is not preferable.

In the case of using a silane coupling agent, water may be added, but the addition is gradually performed after about 15 minutes to 4 hours after the addition of the silane coupling agent and then dropping. There is a need. It is not preferable to add a large amount of water at a time because hydrolysis proceeds rapidly and white turbidity tends to occur. The amount of water to be added is usually in the range of the amount required for hydrolysis of the alkoxy group derived from the silane coupling agent and the remaining alkoxy group derived from the alkoxysilane.
In the step (b), the silica particles and the silane coupling agent need to be sufficiently reacted. Specifically, it is usually necessary to carry out the reaction until the residual amount of the silane coupling agent in the reaction solution is 10% or less with respect to the charged amount. If the reaction between the silica particles and the silane coupling agent remains inadequate and the operation of (c) in the next step is performed, the monomer or oligomer may not be mixed uniformly, or the composition may become cloudy in the subsequent step. It is not preferable. The degree of reaction between the silica particles and the silane coupling agent can be confirmed by measuring the residual amount of the silane coupling agent in the reaction solution.

Step (c) can usually be performed at room temperature (25 ° C.). Moreover, when the viscosity of a monomer or an oligomer is high, or when melting | fusing point of a monomer or an oligomer is room temperature (25 degreeC) or more, you may carry out by heating at 30 to 90 degreeC. The mixing time is preferably 30 minutes to 5 hours.
In the step (d), mainly the solvent used as a liquid medium and the solvent such as alcohol generated by hydrolysis of the alkoxysilane oligomer are removed. However, it may be removed within a necessary range and may not be completely removed. As described above, it is preferably removed to the extent that the composition does not substantially contain a solvent. In addition, when the temperature at the time of removing a solvent is too low, since removal of a solvent is not fully performed, it is unpreferable. Moreover, since it will become easy to gelatinize a composition when it is too high, it is unpreferable. The temperature may be controlled in stages. The removal time is preferably 1 hour to 12 hours. Moreover, it is preferable to remove by reducing the pressure to 20 kPa or less, more preferably 10 kPa or less. However, it is preferable to remove at 0.1 kPa or more. The pressure may be gradually reduced.

  According to the method for producing a radiation curable resin composition to which the present embodiment is applied, a filler (surface-active agent such as silica particles) or a silane coupling agent is added to the resin composition afterwards. Compared with the dispersing method, there is an advantage that ultrafine particles having a smaller particle diameter can be dispersed in a large amount without agglomeration. In addition, the obtained radiation curable resin composition is obtained by dispersing a sufficient amount of silica particles to increase the dimensional stability and mechanical strength of the resin without impairing the radiation transmission. Furthermore, the radiation cured product obtained by curing the radiation curable resin composition has transparency, high surface hardness, and low curing shrinkage. In addition, there is an advantage of having excellent properties that have both dimensional stability and adhesiveness, and further have a degree of surface hardening, and particularly have adhesiveness over time.

(Cured product)
Next, the cured product will be described.
The cured product to which the present embodiment is applied is obtained by irradiating the radiation curable resin composition described above with radiation, and usually has a thickness of 5 cm or less. Preferably it is 1 cm or less, More preferably, it is 1 mm or less, More preferably, it is 500 micrometers or less. However, the film thickness is usually 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, more preferably 30 μm or more, particularly preferably 70 μm or more, and most preferably 85 μm or more.
The transparency of the cured product is preferably 80% or more, more preferably 85% or more, and still more preferably 89% or more, with respect to light having a wavelength of 550 nm, with respect to an optical path length of 0.1 mm. More preferably, the light transmittance per light path length of 0.1 mm in light having a wavelength of 400 nm is preferably 80% or more, more preferably 85% or more, and further preferably 89% or more. Particularly preferably, those having the light transmittance per 1 mm of the optical path length are preferable. The light transmittance is measured at room temperature using, for example, an HP8453 ultraviolet / visible absorptiometer manufactured by Hewlett-Packard Company.

  Moreover, it is preferable that the hardened | cured material to which this Embodiment is applied has surface hardness by the pencil hardness test based on JISK5400 being HB or more, More preferably, it is F or more, More preferably, it is H or more. However, it is preferably 7H or less. In this case, it is preferable that the cured product satisfies the hardness in the above range even in a cured product cured on an inorganic substrate such as glass or metal or a resin substrate. More preferably, the cured product cured on a plastic substrate such as polycarbonate preferably satisfies the above-mentioned range of hardness. If the hardness is too small, it is not preferable because the surface of the cured product is easily damaged. Although there is no problem with the hardness itself being excessively large, the cured product tends to be brittle and is not preferable because cracks and peeling are likely to occur.

  Further, the curing shrinkage of the cured product is preferably as small as possible, and is usually 3% by volume or less, more preferably 2% by volume or less. Curing shrinkage is generally replaced by a method in which a radiation curable resin composition is applied onto a substrate and the amount of concave warpage generated after curing is measured. The measuring method was that a composition film having a thickness of 100 ± 15 microns was formed on a circular polycarbonate plate having a diameter of 130 mm and a thickness of 1.2 ± 0.2 mm using a spin coater, and was irradiated with a prescribed amount of radiation. Then, leave it on the surface plate for 1 hour. After standing, the concave warp of the polycarbonate plate caused by the curing shrinkage of the composition is measured. The concave warp is preferably 1 mm or less, more preferably 0.1 mm or less.

Furthermore, the smaller the thermal expansion of the cured product, the better the dimensional stability, which is preferable. For example, the smaller the linear expansion coefficient, which is one of the specific indicators of thermal expansion, is preferable, and it is usually preferably 13 × 10 ⁻⁵ / ° C. or less, more preferably 12 × 10 ⁻⁵ / ° C. or less, and still more preferably 10 × 10 ⁻⁵ / ° C. or less, particularly preferably 8 × 10 ⁻⁵ / ° C. or less. The linear expansion coefficient is, for example, a weight of 1 g by a compression method thermomechanical measurement (TMA; SSC / 5200 type; manufactured by Seiko Instruments Inc.) using a plate-shaped test piece of 5 mm × 5 mm × 1 mm, and a heating rate of 10 The linear expansion coefficient is evaluated in 10 ° C increments in the range from 40 ° C to 100 ° C, and the average value can be used as a representative value.

Moreover, the one where the adhesiveness with respect to the predetermined gas of hardened | cured material is higher is preferable. The adhesion is measured by dropping 15 drops of the composition on a 10 cm square optically polished glass plate using a dropper, leaving it at room temperature for 1 minute, irradiating a specified amount of radiation, and then leaving it at room temperature for 1 hour. To cure. A cut is made in the center of the cured composition portion with a cutter knife so that it reaches the glass surface. After leaving for 14 days at room temperature, the peeling of the interface between the cured product and the glass surface is visually observed. It was evaluated based on the following criteria. Note that the number of samples is five.
A: No peeling was observed for all samples.
○: No peeling was observed for two or more samples.
Δ: No peeling was observed in only the sample of 1.
X: Peeling was visually observed for all samples.
As adhesiveness of hardened | cured material, (circle) or (double-circle) is preferable and (double-circle) is still more preferable. Moreover, what has the adhesiveness mentioned above with respect to plastic substrates, such as a polycarbonate, is still more preferable than on an optical polishing glass plate.

Further, the hardened surface is preferably harder. The method of measuring the degree of surface curing is to irradiate the radiation curable resin composition with a specified amount of ultraviolet light and cure it, then use a right index finger and thumb wearing rubber gloves to place the sample so that the thumb is on the coated surface side. The surface condition of the cured product was evaluated based on the following criteria when lightly sandwiched and the thumb was separated from the coating surface.
○: No thumb mark is visually observed.
(Triangle | delta): A thumb mark is observed thinly visually.
X: A thumb mark is deeply observed visually.
The degree of surface curing of the cured product is preferably ◯.

(Radiation curing conditions)
Next, radiation curing conditions for obtaining a cured product to which the present embodiment is applied will be described.
In the cured product to which the present embodiment is applied, the radiation curable resin composition is irradiated with radiation (active energy rays or electron beams) to initiate a polymerization reaction of the monomer having a radiation curable group and / or its oligomer. It is obtained by so-called “radiation curing”. There is no restriction | limiting in the form of a polymerization reaction, For example, well-known polymerization forms, such as radical polymerization, anionic polymerization, cation polymerization, and coordination polymerization, can be used. Among these polymerization modes, the most preferable polymerization mode is radical polymerization. The reason for this is not clear, but it is presumed to be due to the homogeneity of the product due to the initiation of the polymerization reaction being homogeneous and proceeding in a short time within the polymerization system.

The radiation applied to the radiation curable resin composition is an electromagnetic wave (gamma ray, X-ray, ultraviolet ray, visible ray, infrared ray, microwave, etc.) that acts to generate a chemical species that acts on the polymerization initiator to initiate the polymerization reaction. Or a particle beam (an electron beam, an alpha ray, a neutron beam, various atomic beams, etc.). Examples of radiation preferably used are active energy rays and general-purpose light sources. Specifically, ultraviolet rays, visible rays, and electron beams are preferable, and ultraviolet rays and electron beams are most preferable.
When ultraviolet rays are used, a method using a photo radical generator as a polymerization initiator is employed. At this time, you may use a sensitizer together as needed. Ultraviolet rays are usually in a wavelength range of 200 nm to 400 nm, preferably 250 nm to 400 nm. As a device for irradiating ultraviolet rays, a known device such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet lamp having a structure for generating ultraviolet rays by microwaves can be preferably used. The output of the apparatus for irradiating ultraviolet rays is usually 10 W / cm to 200 W / cm. In addition, it is preferable to install the apparatus at a distance of 5 cm to 80 cm with respect to the irradiated body because there is little light deterioration, thermal deterioration, thermal deformation and the like of the irradiated body.

  The cured product to which the present embodiment is applied can be preferably cured by irradiating the above-described radiation curable resin composition with an electron beam, and a cured product having excellent mechanical properties, particularly tensile elongation properties, is obtained. be able to. When an electron beam is used, the light source and irradiation device of the electron beam are expensive, but the addition of an initiator can be omitted, and the degree of surface hardening of the cured product is good without being subjected to polymerization inhibition by oxygen. Therefore, it may be preferably used. An electron beam irradiation apparatus used for electron beam irradiation is not particularly limited, and examples thereof include a curtain type, an area beam type, a broad beam type, and a pulse beam type. The acceleration voltage during electron beam irradiation is preferably 10 kV to 1000 kV.

Intensity of radiation, usually, 0.1 J / cm ² or more, preferably irradiated with 0.2 J / cm ² or more energy. However, usually, it irradiated at 20 J / cm ² or less energy range, preferably 10J / cm ² or less, more preferably 5 J / cm ² or less, more preferably 3J / cm ² or less, particularly preferably 2J / cm ² or less Irradiate with. If the radiation intensity is within this range, it can be appropriately selected depending on the type of the radiation curable resin composition. For example, in the case of a radiation curable resin composition containing a monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof, the irradiation intensity is preferably ² J / cm ² or less. In the case of a radiation curable resin composition containing a monomer comprising a condensed alicyclic acrylate and / or an oligomer thereof, the radiation irradiation intensity is preferably ³ J / cm ² or less.
When the irradiation energy and irradiation time of the radiation are extremely small, the heat resistance and mechanical properties of the crosslinked resin composition may not be sufficiently exhibited because the polymerization reaction is incomplete. The irradiation time is usually 1 second or longer, preferably 10 seconds or longer. However, when the irradiation time is excessively long, deterioration such as a decrease in hue due to light such as yellowing may occur. Therefore, the irradiation time is usually 3 hours or less, and preferably about 1 hour or less in terms of reaction acceleration and productivity.

  The irradiation of radiation may be performed in one stage or in a plurality of stages. As a radiation source, a radiation source in which radiation spreads in all directions is used. Usually, the radiation curable resin composition shaped in a mold is fixed in a stationary state or conveyed by a conveyor. Irradiate with the source stationary. It is also possible to cure the coating liquid film of the radiation curable resin composition coated on a suitable substrate (for example, resin, metal, semiconductor, glass, paper, etc.) by irradiation with radiation.

(Laminate)
Next, a laminated body is demonstrated.
In the laminate to which the present embodiment is applied, the above-described cured product is laminated on the adherend. The above-mentioned cured product is excellent in transparency, surface curing property, dimensional stability, adhesion, strength, low curing shrinkage, heat resistance, etc., and a laminate comprising this cured product as a constituent layer is used for various films and coatings. Used for. A particularly preferable specific example of the laminate is an optical recording medium.
The adherend is not particularly limited, and examples thereof include resins, glass, ceramics, inorganic crystals, metals, semiconductors, diamond, organic crystals, paper pulp, and wood. Among these, a plastic substrate such as polycarbonate and a substrate in which an organic substance or an inorganic substance is laminated on the plastic substrate are preferable.
The glass transition temperature of the cured product used for the laminate is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 170 ° C. or higher. The glass transition temperature is usually measured by differential thermal analysis (DSC), thermomechanical measurement (TMA) or dynamic viscoelasticity measurement.
Moreover, it is preferable that the hardened | cured material used for a laminated body does not melt | dissolve with respect to various solvents. Typically, it is preferable not to dissolve in a solvent such as toluene, chloroform, acetone, or tetrahydrofuran.

The cured product used for the laminate contains inorganic substance ultrafine particles such as silica particles, and such inorganic substance ultrafine particles are substances having optical properties different from those of the organic resin matrix. For this reason, the cured product as a whole may have a unique balance between the refractive index and the Abbe number that cannot be realized by an organic material alone. Such a balance between the peculiar refractive index and the Abbe number may be useful in an application in which refraction of light such as a lens or a prism is desired and birefringence is desired to be small. Specifically, the constant term C in the following formula representing the relationship between the refractive index n _D and the Abbe number ν _D measured at 23 ° C. at the sodium D-line wavelength deviates from the range of 1.70 to 1.82. This is the case.

In general, in a molded body using a resin material, the birefringence increases as the thickness increases. On the other hand, the cured product used in the laminate to which the present embodiment is applied, by using silane-treated silica particles, has an unprecedented rate of increase in birefringence for the increase in the thickness of the cured product. In some cases, the feature of obtaining a small value is acquired. Therefore, when the cured product is used as a relatively thick molded body having a thickness of 0.1 mm or more like an optical member described later, it is advantageous in terms of lowering the birefringence.
The cured product used for the laminate to which the present embodiment is applied usually exhibits insoluble properties in solvents and the like, and has properties that are advantageous for applications such as optical members even when it is thickened. It is preferable that the property and the degree of surface hardening are excellent. Specifically, it is preferable to exhibit low optical distortion (low birefringence), high light transmittance, dimensional stability, high adhesion, high degree of surface curing, and a certain level of heat resistance. Further, the smaller the curing shrinkage, the better.

  In the laminate to which the present embodiment is applied, a cured product layer having a film thickness of 100 ± 15 μm is formed on an adherend, and this is formed in an environment of 80 ° C. and 85% RH for 100 hours, preferably 200. It is preferable to maintain that the ratio of the adhesion area to the adherend after placing for a time is 50% or more, preferably 80% or more, particularly preferably 100% of the initial adhesion area.

  In the laminate to which the present embodiment is applied, the adhesiveness of the cured product to the adherend is set to a film thickness of 100 by curing the radiation curable resin composition applied to the surface of the 10 cm square adherend. A laminate having a cured product layer of ± 15 μm is formed, and this laminate is placed in a constant temperature and humidity chamber set at 80 ° C. and 85% RH for 100 hours, and then a transparent 2 cm grid is drawn on the taken out laminate. The percentages of the total number of squares having a peel area with respect to the adherend of less than half are overlapped, and the percentage of the adhesion area with respect to the adherend can be obtained. Or it can obtain | require by measuring the weight of the adherend with a composition film | membrane before and after a constant temperature and humidity test.

(Optical material)
Next, the optical material will be described.
The cured product described above has excellent performance as an optical material because it has a small optical distortion represented by birefringence, good transparency, and excellent functional properties such as dimensional stability and surface hardness. ing. The optical material here refers to the optical properties of the material, such as transparency, light absorption and emission characteristics, difference in refractive index from the outside, small birefringence, balance between the above-mentioned unique refractive index and Abbe number, etc. It refers to general molded products used for applications. Specific examples include display panels, touch panels, lenses, prisms, waveguides, optical amplifiers and other optics, and optoelectronic members.
The optical materials to which this embodiment is applied are roughly classified into the following two types. The first optical material is an optical material that is a molded body of a cured product, and the second optical material is an optical material that is a molded body having a thin film of the cured product as a part of the layer. In the former, the main component of the optical material is a cured product, and in addition, an arbitrary thin film (coat layer) of a material other than the cured product may be included. On the other hand, in the latter, the main component of the optical material is composed of a material other than the precured material, and has a thin film of the cured material as a part of the layer. Any optical material may be formed in close contact with an arbitrary solid material substrate such as resin, glass, ceramics, inorganic crystal, metal, semiconductor, diamond, organic crystal, paper pulp, and wood.

Although there is no restriction | limiting in the dimension of a 1st optical material, The optical path length of the part of hardened | cured material is 0.01 mm in terms of the mechanical strength of an optical material, Preferably it is 0.1 mm, Preferably it is 0.1 mm, More preferably 0.2 mm. On the other hand, the upper limit is usually 10,000 mm, preferably 5000 mm, and more preferably 1000 mm in terms of attenuation of light intensity.
The shape of the first optical material is not limited, but examples thereof include a plate shape, a curved plate shape, a lens shape (concave lens, convex lens, concavo-convex lens, half-concave lens, half-convex lens, etc.), prism shape, fiber shape, and the like. Is done.

Although there is no restriction | limiting in the dimension of a 2nd optical material, The film thickness of the thin film of hardened | cured material is 0.05 micrometer normally in terms of mechanical strength or an optical characteristic, Preferably it is 0.1 micrometer, More preferably 0.5 μm. On the other hand, the upper limit value of the film thickness is usually 3000 μm, preferably 2000 μm, more preferably 1000 μm, from the viewpoint of thin film forming processability and cost-effectiveness balance.
There is no limitation on the shape of such a thin film, but it is not necessarily flat. For example, it is formed on a substrate having an arbitrary shape such as a spherical shape, an aspherical curved surface shape, a cylindrical shape, a conical shape, or a bottle shape. It may be.
In the optical material to which the present embodiment is applied, if necessary, any coating layer, for example, a protective layer that prevents mechanical damage to the coated surface due to friction or wear, deterioration of semiconductor crystal particles or a substrate, etc. A light absorbing layer that absorbs light with an undesirable wavelength that causes it, a transmission shielding layer that suppresses or prevents transmission of reactive low molecules such as moisture and oxygen gas, an antiglare layer, an antireflection layer, a low refractive index layer, etc. An optional additional functional layer such as an undercoat layer or an electrode layer for improving the adhesion between the substrate and the coated surface may be provided to form a multilayer structure. Specific examples of the optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, and a gas barrier film and hard coat made of an organic coating layer. As a coating method for an arbitrary coating layer, a known coating method such as a vacuum deposition method, a CVD method, a sputtering method, a dip coating method, or a spin coating method can be used.

  Specific examples of the optical material to which the present embodiment is applied are described in more detail. For example, various lenses such as a lens for spectacles, a microlens for an optical connector, a condensing lens for a light emitting diode, an optical switch, an optical fiber, and an optical circuit Optical communication parts such as optical branching, junction circuit, optical multiple branching circuit, luminous intensity adjuster, etc., various display members such as liquid crystal substrates, touch panels, light guide plates, phase difference plates, optical disk substrates and optical film coatings Applications for storage and recording, optical communication materials such as optical adhesives, functional films, antireflection films, optical multilayer films (selective reflection films, selective transmission films, etc.), super-resolution films, ultraviolet absorption films, reflections Examples include various optical films and coating applications such as a control film, an optical waveguide, and an identification function printing surface.

(Optical recording medium)
Next, an optical recording medium to which the present embodiment is applied will be described with reference to the drawings. FIG. 1 is a diagram illustrating an example of an optical recording medium. FIG. 1 shows a rewritable optical recording medium 10. In the optical recording medium 10, a substrate 1, a recording / reproducing functional layer 5 formed on the substrate 1, and a protective layer 3 are sequentially laminated. The recording / reproducing functional layer 5 is provided so as to sandwich the reflective layer 51 formed of a metal material directly provided on the substrate 1, the recording layer 53 formed of a phase change material, and the recording layer 53 from above and below. And two dielectric layers 52 and 54. The optical recording medium 10 normally records and reproduces optical information using a laser beam having a wavelength of 380 nm to 800 nm, preferably a laser beam having a wavelength of 450 nm to 350 nm, and is not particularly limited. A next-generation high-density optical recording medium using a laser may be mentioned.

  On one main surface of the substrate 1, an uneven groove for use in recording / reproducing optical information is provided, for example, formed by injection molding of a light-transmitting resin using a stamper. Although the material of the board | substrate 1 will not be specifically limited if it is a light transmissive material, For example, thermoplastic resins, such as polycarbonate resin, polymethacrylate resin, and polyolefin resin, and glass can be used. Of these, polycarbonate resin is most preferred because it is most widely used in CD-ROMs and is inexpensive. The thickness of the substrate 1 is usually 0.1 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more, on the other hand, 20 mm or less, preferably 15 mm or less, more preferably 3 mm or less. It is about 1.2 ± 0.2 mm. The outer diameter of the substrate 1 is generally about 130 mm.

  The recording / reproducing functional layer 5 is a layer configured to exhibit a function capable of recording / reproducing an information signal or reproducing the information signal, and may be a single layer or a plurality of layers. The recording / reproducing functional layer 5 can repeatedly perform recording and erasure when the optical recording medium is a reproduction-only medium (ROM medium) and when the optical recording medium is a write-once medium (Write Once medium) that can be recorded only once. Depending on the case of a rewritable medium (Rewriteable medium), it is possible to adopt a layer structure corresponding to each purpose.

  For example, in a read-only medium, the recording / reproducing functional layer 5 is usually composed of a single layer containing a metal such as Al, Ag, Au, etc. For example, the recording / reproducing functional layer 5 is made of Al, Ag by sputtering. The Au reflection layer 51 is formed on the substrate 1.

  In the write-once type medium, the recording / reproducing functional layer 5 is usually formed by providing a reflective layer 51 containing a metal such as Al, Ag, Au, etc. and a recording layer 53 containing an organic dye on the substrate 1 in this order. Composed. Examples of such a write-once medium include a medium in which the reflective layer 51 is provided by a sputtering method and then an organic dye layer is formed on the substrate 1 by a spin coating method. As another specific example of the write-once medium, the recording / reproducing functional layer 5 includes a reflective layer 51 containing a metal such as Al, Ag, Au, a dielectric layer 52, a recording layer 53, and a dielectric layer. The body layer 54 may be provided on the substrate 1 in this order, and the dielectric layer 52 and the recording layer 53 may contain an inorganic material. In such a write-once medium, the reflective layer 51, the dielectric layer 52, the recording layer 53, and the dielectric layer 54 are usually formed by sputtering.

  In the rewritable medium, the recording / reproducing functional layer 5 is generally composed of a reflective layer 51 containing a metal such as Al, Ag, Au, a dielectric layer 52, a recording layer 53, and a dielectric layer 54. Generally, the dielectric layer 52 and the recording layer 53 contain an inorganic material by being provided on the substrate 1 in this order. In such a rewritable medium, the reflective layer 51, the dielectric layer 52, the recording layer 53, and the dielectric layer 54 are usually formed by sputtering. Another specific example of the rewritable medium is a magneto-optical recording medium. In the recording / reproducing function layer 5, a recording / reproducing area is set. The recording / reproducing area is usually provided in an area having an inner diameter larger than the inner diameter of the recording / reproducing functional layer 5 and an outer diameter smaller than the outer diameter of the recording / reproducing functional layer 5.

The material used for the reflective layer 51 is preferably a substance having a high reflectivity, and in particular, a metal such as Au, Ag, or Al that can be expected to have a heat dissipation effect. A small amount of metal such as Ta, Ti, Cr, Mo, Mg, V, Nb, Zr, or Si may be added to control the thermal conductivity of the reflective layer 51 itself or to improve the corrosion resistance. The amount of metal added in a small amount is usually 0.01 atomic% or more and 20 atomic% or less. Among them, an aluminum alloy containing 15 atomic% or less of Ta and / or Ti, in particular, an alloy of Al _α Ta _1-α (where 0 ≦ α ≦ 0.15) is excellent in corrosion resistance, and optical This is a particularly preferable material for the reflective layer 51 in order to improve the reliability of the recording medium. An Ag alloy containing any one of Mg, Ti, Au, Cu, Pd, Pt, Zn, Cr, Si, Ge, and rare earth elements in an amount of 0.01 atomic% to 10 atomic% is a reflectance. High thermal conductivity and excellent heat resistance are preferable.

  The thickness of the reflective layer 51 is usually 40 nm or more, preferably 50 nm or more, and is usually 300 nm or less, preferably 200 nm or less. If the thickness of the reflective layer 51 is excessively large, the shape of the tracking groove formed in the substrate 1 changes, and further, it takes time to form a film and the material cost tends to increase. Further, when the thickness of the reflective layer 51 is excessively small, not only does the light transmission occur and the reflective layer 51 does not function, but also an influence of an island-like structure formed in the initial stage of film growth tends to occur on a part of the reflective layer 51. The reflectance and thermal conductivity may be reduced.

  The materials used for the two dielectric layers 52 and 54 are used to prevent evaporation / deformation accompanying the phase change of the recording layer 53 and to control thermal diffusion at that time. The material of the dielectric layer 52 or the dielectric layer 54 is determined in consideration of the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, and the like. In general, dielectric materials such as oxides, sulfides, nitrides, carbides, and fluorides such as Ca, Mg, and Li, which are highly transparent and have a high melting point, can be used. These oxides, sulfides, nitrides, carbides, and fluorides do not necessarily have to have a stoichiometric composition, and it is also effective to control the composition for controlling the refractive index, or to mix them. is there.

  Specific examples of such dielectric materials include, for example, Sc, Y, Ce, La, Ti, Zr, Hf, V, Nb, Ta, Zn, Al, Cr, In, Si, Ge, Sn, Sb and Metal oxides such as Te; nitriding metals such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, B, Al, Ga, In, Si, Ge, Sn, Sb and Pb Examples thereof include carbides of metals such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, B, Al, Ga, In, and Si, or mixtures thereof. In addition, metal sulfides such as Zn, Y, Cd, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi; selenides or tellurides; fluorides such as Mg and Ca, or a mixture thereof be able to.

In consideration of repetitive recording characteristics, a mixture of dielectrics is preferable. For example, a mixture of a chalcogen compound such as ZnS or rare earth sulfide and a heat-resistant compound such as oxide, nitride, carbide, or fluoride can be used. For example, a mixture of a heat-resistant compound mainly composed of ZnS and a mixture of a rare-earth sulfate, particularly a heat-resistant compound mainly composed of Y ₂ O ₂ S, are examples of a preferable dielectric layer 52 or dielectric layer 54 composition. is there. More specifically, ZnS—SiO ₂ , SiN, SiO ₂ , TiO ₂ , CrN, TaS ₂ , Y ₂ O ₂ S and the like can be mentioned. Among these materials, ZnS—SiO ₂ is widely used because of its high film formation rate, low film stress, small volume change rate due to temperature change, and excellent weather resistance. The thickness of the dielectric layer 52 or the dielectric layer 54 is usually 1 nm or more and 500 nm or less. By setting the thickness to 1 nm or more, the deformation preventing effect of the substrate 1 and the recording layer 53 can be sufficiently secured, and the role as the dielectric layer 52 or the dielectric layer 54 can be sufficiently fulfilled. Further, when the thickness is 500 nm or less, the internal layer of the dielectric layer 52 or the dielectric layer 54 itself, the difference in elastic characteristics from the substrate 1 or the like is remarkable while sufficiently serving as the dielectric layer 52 or the dielectric layer 54. Thus, the occurrence of cracks can be prevented.

Examples of the material for forming the recording layer 53 include compounds having a composition such as GeSbTe, InSbTe, AgSbTe, AgInSbTe. Among them, {(Sb ₂ Te ₃ ) _1-x (GeTe) _x } _1-y Sb _y (0.2 ≦ x ≦ 0.9, 0 ≦ y ≦ 0.1) alloy or (Sb _x Te _{1 — x} ) _y M _1-y (where 0.6 ≦ x ≦ 0.9, 0.7 ≦ y ≦ 1, M is Ge, Ag, In, Ga, Zn, Sn, Si, Cu, Au, Pd, A thin film mainly composed of an alloy (which is at least one selected from Pt, Pb, Cr, Co, O, S, Se, V, Nb, Ta) is stable in both crystalline and amorphous states, A fast phase transition between both states is possible. Furthermore, there is an advantage that segregation hardly occurs when repeated overwriting, and it is the most practical material.

  The film thickness of the recording layer 53 is usually 5 nm or more, preferably 10 nm or more. With such a range, a sufficient optical contrast between the amorphous state and the crystalline state can be obtained. Further, the film thickness of the recording layer 53 is usually 30 nm or less, preferably 20 nm or less. With such a range, it is possible to obtain an increase in optical contrast due to the light transmitted through the recording layer 53 being reflected by the reflective layer 51, and the heat capacity can be controlled to an appropriate value. Recording can also be performed. In particular, if the thickness of the recording layer 53 is 10 nm or more and 20 nm or less, it is possible to achieve both higher speed recording and higher optical contrast. By setting the thickness of the recording layer 53 in such a range, the volume change due to the phase change is reduced, and the recording layer 53 itself and other layers in contact with the upper and lower sides of the recording layer 53 are repeatedly overwritten repeatedly. The effect of volume change can be reduced. Further, accumulation of irreversible microscopic deformation of the recording layer 53 is suppressed, noise is reduced, and repeated overwrite durability is improved.

  The reflective layer 51, the recording layer 53, the dielectric layer 52, and the dielectric layer 54 are usually formed by a sputtering method or the like. It is possible to form a film with an in-line apparatus in which a target for the recording layer 53, a target for the dielectric layer 52 or the dielectric layer 54, and, if necessary, a target for the material of the reflective layer 51 are installed in the same vacuum chamber. This is desirable in terms of preventing oxidation and contamination. It is also excellent in terms of productivity.

  The protective layer 3 is made of a cured product obtained by spin-coating the radiation curable resin composition described above and curing it, and is provided in contact with the recording / reproducing functional layer 5 and has a planar annular shape. The protective layer 3 is made of a material that can transmit laser light used for recording and reproduction. The transmittance of the protective layer 3 is usually 80% or more, preferably 85% or more, and more preferably 89% or more at the wavelength of light used for recording / reproduction. Within such a range, loss due to absorption of recording / reproducing light can be minimized. On the other hand, the transmittance is most preferably 100%, but is usually 99% or less because of the performance of the material used.

Such a photocurable resin is sufficiently transparent to blue laser light having a wavelength of about 405 nm used for recording / reproducing of an optical disk, and protects the recording layer 53 formed on the substrate 1 from water and dust. It is desirable to have such properties.
Further, the surface hardness of the protective layer 3 is preferably HB or more, more preferably F or more, and still more preferably H or more, according to a pencil hardness test in accordance with JIS K5400. However, it is preferably 7H or less. If the hardness is too small, it is not preferable because the surface is easily scratched. Although there is no problem with the hardness being too large, the cured product tends to become brittle, and cracks and peeling are likely to occur, which is not preferable.
Furthermore, it is preferable that the adhesion between the protective layer 3 and the recording / reproducing functional layer 5 is high. Furthermore, it is preferable that the adhesiveness with time is higher, and the ratio of the adhesive area between the protective layer 3 and the recording / reproducing functional layer 5 after being placed in an environment of 80 ° C. and 85% RH for 100 hours, more preferably 200 hours is It is preferable to hold 50% or more of the contact area. More preferably, it is 80% or more, and particularly preferably 100%.
The thickness of the protective layer 3 is usually 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, still more preferably 70 μm or more, and particularly preferably 85 μm or more. When the film thickness is in such a range, the influence of dust and scratches attached to the surface of the protective layer 3 can be reduced, and the thickness is sufficient to protect the recording / reproducing functional layer 5 from moisture of the outside air. It can be. On the other hand, it is usually 300 μm or less, preferably 130 μm or less, more preferably 115 μm or less. When the film thickness is within this range, a uniform film thickness can be easily formed by a general coating method used in spin coating or the like. The protective layer 3 is preferably formed with a uniform film thickness in a range covering the recording / reproducing functional layer 5.

The film thickness of the protective layer 3 has an important influence on the performance of the objective lens used for recording and reproduction. The objective lens is designed in consideration of the thickness of the protective layer 3. Therefore, the thickness of the protective layer 3 needs to be strictly set to the thickness determined by the design value of the objective lens according to the optical refractive index. From the viewpoint of obtaining good convergent light by reducing the spherical aberration of the objective lens, the thickness of the protective layer 3 is usually within ± 5% of the average thickness, and preferably within ± 3%. For example, when an objective lens designed with a blue laser beam of 405 nm, a lens aperture ratio (NA) of 0.85, and a refractive index n = 1.5 of the protective layer 3 is used as a recording / reproducing system, wavefront aberration can be ignored. In order to make it as small as possible, the film thickness of the protective layer 3 must be controlled within a range of ± 5% of the average film thickness, preferably within ± 4%, and more preferably within ± 3%.
The optical recording medium 10 obtained in this way may be used as a single plate, or two or more may be bonded together. In addition, a hub may be attached if necessary and incorporated into the cartridge.

Hereinafter, the present embodiment will be described in more detail based on examples. The present embodiment is not limited to the examples.
(Evaluation methods)
(1) Quantitative determination method of residual silane coupling agent A column (J & W DB-5) was installed in a gas chromatography device (GC14B, Shimadzu Corporation), helium was used as the carrier gas, and the column temperature rising pattern was 40 ° C. → 220 ° C. (10 minutes hold) → 250 ° C. → 290 ° C. (10 minutes hold) However, the temperature increase rate from 40 ° C. to 220 ° C. is 10 ° C. per minute, the temperature increase rate from 220 ° C. to 250 ° C. is 5 ° C. per minute, and the temperature increase rate from 250 ° C. to 290 ° C. is 10 ° C. per minute. did. The measurement was performed by adding a composition sample to an internal standard solution (meta-xylene) having a weight of about 1/150 of the composition sample weight as a measurement sample and an injection amount of about 0.3 microliters.
(2) Method for quantifying silica particles First, the total amount of silicon atoms S (mol) was quantified using a fluorescent X-ray analysis method. As a sample, a drop of the composition liquid sample diluted 100 times on a filter paper was used.
Next, the ²⁹ Si-NMR method was used to determine the ratio of silicon atoms derived from silica particles in the total silicon atoms. The number of integrations was 2000. In the obtained spectrum, when the peak of tetramethylsilane is based on 0 ppm, the chemical shift derived from the silane coupling agent is -20 ppm to less than −80 ppm in total signal area (m), and the chemical derived from silica particles The total area (n) of signals observed at a shift of −80 ppm to −120 ppm was determined, and the silicon atom ratio derived from silica particles in the total silicon atoms was determined according to the following formula.
p (mol) = m / (m + n)
(3) Composition transparency The composition immediately after production was visually evaluated.
(4) Storage stability The composition 10g was put into the glass container with a lid | cover, and it preserve | saved in the oven set to 40 degreeC with the lid | cover. Observation was carried out every day for two weeks from the day after the start of storage, and it was examined whether or not it was clouded by visual observation. When cloudiness was confirmed, the number of days until the day before the confirmed date was defined as storage stability.

(Example 1)
(A) Preparation of tetramethoxysilane oligomer After mixing 234 g of tetramethoxysilane and 74 g of methanol, 22.2 g of 0.05% hydrochloric acid was added, and a hydrolysis reaction was performed at 65 ° C. for 2 hours. Next, the system temperature was raised to 130 ° C., and the produced methanol was removed. Then, the temperature was gradually raised to 150 ° C. while blowing nitrogen gas, and the tetramethoxysilane monomer was removed by keeping it for 3 hours.
(B) Preparation of silica particles After adding 62.4 g of methanol to 30.8 g of the tetramethoxysilane oligomer obtained by the operation of (a) and stirring uniformly, 0.31 g of acetylacetone aluminum was dissolved as a catalyst. To this solution, 6.5 g of demineralized water was gradually added dropwise with stirring, and the mixture was stirred at 60 ° C. for 2 hours to grow silica particles. The diameter of the produced silica particles was 2 nm to 5 nm by morphological observation using a TEM electron microscope.
(C) Hydrophobization treatment of silica particle surface with silane coupling agent 15 g of acryloyloxypropyltrimethoxysilane as a silane coupling agent is added to 40 g of an alcohol solution of silica particles obtained by the operation of (b) The mixture was stirred for 2 hours, and the silane coupling agent was reacted with the surface of the silica particles to obtain 55 g of a silane-treated silica particle solution.
(D) Synthesis of oligomer of monomer unit compound having urethane bond 60.8 g of isophorone diisocyanate and 10 mg of dibutyltin laurate are placed in a four-necked flask and heated to 70 to 80 ° C. in an oil bath, and the temperature becomes constant. Gently stir until When the temperature becomes constant, a mixture of 12.2 g of dimethylolbutanoic acid and 45.3 g of polytetramethylene ether glycol is dropped with a dropping funnel, and the mixture is stirred for 2 hours while maintaining the temperature at 70 ° C. Subsequently, a mixture of 31.8 g of hydroxyethyl acrylate and 0.1 g of methoquinone was dropped with a dropping funnel and stirred for 15 hours to synthesize 150 g of a carboxyl group-containing urethane acrylate oligomer. This carboxyl group-containing urethane acrylate oligomer contained 30% by weight of a constitution derived from polytetramethylene ether glycol.
(E) Preparation of radiation curable composition A dilution obtained by adding 50 g of acryloylmorpholine to 150 g of the carboxyl group-containing urethane acrylate oligomer obtained by (d) to 50 g of the silane-treated silica particle solution obtained by the operation of (c). 38.3 g of the liquid and 2.7 g of 1-hydroxycyclohexyl phenyl ketone as a photo radical generator were added and stirred at room temperature for 2 hours to obtain a transparent radiation curable resin composition.
The low boiling point component contained in this radiation curable resin composition was removed by evaporation under reduced pressure at 30 ° C. for 2 hours and further at 40 ° C. for 1 hour. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition. No white turbidity was observed in the composition, and high transparency and high storage stability were exhibited.

(Example 2)
In Example 1, a radiation curable resin composition was obtained by performing the same conditions and operations as in Example 1 except that the reaction condition of the silane coupling agent was changed to 75 ° C. for 1 hour. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition. No white turbidity was observed in the composition, and it showed high transparency. It also showed high storage stability.

(Example 3)
In Example 1, instead of 15 g of acryloyloxypropyltrimethoxysilane, the same conditions and operations as in Example 1 were used except that a mixture of 10 g of methyltrimethoxysilane and 5 g of acryloyloxypropyltrimethoxysilane was used. A resin composition was obtained. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition. No white turbidity was observed in the composition, and it showed high transparency. It also showed high storage stability.

(Comparative Example 1)
A radiation curable resin composition was obtained by performing the same conditions and operations as in Example 1 except that the reaction condition of the silane coupling agent was 2 hours at room temperature. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition. White turbidity was observed in the composition.

(Comparative Example 2)
A radiation curable resin composition was obtained by carrying out the same conditions and operations as in Example 1 except that the reaction condition of the silane coupling agent was changed to 60 ° C. for 2 hours. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition. Although no cloudiness was observed in the composition and the transparency was high, the storage stability was low.

(Comparative Example 3)
A radiation curable resin composition was obtained by performing the same conditions and operations as in Example 3 except that the reaction condition of the silane coupling agent was changed to 60 ° C. for 2 hours. Table 1 shows the amount ratio (A) of the unreacted silane coupling agent, composition transparency, and storage stability of the obtained radiation-curable resin composition.
No white turbidity was observed in the composition and the transparency was high, but the storage stability was low.

  From the results shown in Table 1, it contains silane-treated silica particles surface-treated by reacting silica particles with a silane coupling agent, a monomer having a radiation curable group, and / or an oligomer thereof, It can be seen that the radiation curable resin compositions (Example 1 to Example 3) in which the amount ratio (A) of the silane coupling agent in the reaction is 6% by weight or less ensure high transparency and storage stability. .

It is a figure explaining an example of an optical recording medium.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 3 ... Protective layer, 5 ... Recording / reproducing functional layer, 10 ... Optical recording medium, 51 ... Reflective layer, 52, 54 ... Dielectric layer, 53 ... Recording layer

Claims (9)

Silane-treated silica particles surface-treated by reacting 20 parts by weight or more of a silane coupling agent with respect to 100 parts by weight of silica particles;
A monomer having a radiation curable group and / or an oligomer thereof,
A radiation curable resin composition, wherein the amount ratio (A) of the unreacted silane coupling agent represented by the following formula is 6% or less.

  2. The radiation curable resin composition according to claim 1, wherein the content of the silane-treated silica particles having a particle size larger than 30 nm is 1% by weight or less.   The radiation curable resin composition according to claim 1, wherein the silica particles are obtained by a hydrolysis reaction of an oligomer of alkoxysilane. The radiation curable resin composition according to any one of claims 1 to 3, wherein the silane coupling agent is a compound represented by the following formula (1).

(In formula (1), R is an alkyl group, R ′ is a group containing a reactive group, and Q ¹ and Q ² are each independently a monovalent organic group.)   Production of a radiation curable resin composition comprising a step of preparing silane-treated silica particles by reacting 20 parts by weight or more of silane coupling agent with respect to 100 parts by weight of silica particles at a temperature of 70 ° C. or more. Method.   Hardened | cured material formed by hardening | curing the radiation-curable resin composition of any one of Claims 1 thru | or 4.   The cured product according to claim 6, which is used for an optical material.   The laminated body which has the hardened | cured material of Claim 6 or 7 laminated | stacked on the board | substrate.   An optical recording medium having a layer comprising the cured product according to claim 6.

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