JPH06134772A - Optical component - Google Patents

Abstract

PURPOSE:To mold a transparent material having a low viscosity, a high refractive index, and a low absorptivity so as to manufacture optical components at a low cost by adding a compound to be indicated by a specific general formula in an acrylic and metacrylic resin composition for a specific quantity. CONSTITUTION:A compound of 5-100 pts.wt. shown in the formula I is added to an acrylic and metacrylic resin composition. The acrylic and metacrylic resin composition is arranged in a matrix, cured by heat or energy rays, and the resin composition and the matrix are peeled so as to form optical parts. In this way, the workability at manufacturing is excellent due to a material having colorless transparency, low viscosity, high refractive index, and low absorptivity, so that optical components having high efficiency can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of optical parts from acrylic and methacrylic resin compositions or combinations of these with transparent molded articles.

[0002]

2. Description of the Related Art In order to manufacture a projection type screen for television, a general Fresnel lens, a general lens, an optical disk substrate, a diffraction grating, etc., transfer is carried out from a mother die having irregularities or a constant curved surface, and a large number of optical elements Forming parts is being done.

There are the following two methods for manufacturing this kind of optical component.

The first method is, as shown in FIG.
Resin (4) is injected from the inlet (3) into the space (2) formed by (1a, 1b), and the resin is cured by heat or energy rays, and then an optical component composed of the cured resin (4). (5a) is obtained [eg T. Kaetu et al: J. Appl. Polymer Sci. 24 1515
(1979), JP-A-59-141, etc.].

In the second method, as shown in FIG. 2, the photocurable resin (4) is placed in the space (2) between the transparent molding (6) and the mother die (1c).
, And the resin is cured with heat or energy rays, and then
(1c) is peeled off and the transparent molded product (6) and the photocurable resin cured product
An optical component (5b) composed of (4) is obtained (JP-A-53-86).
756, JP 61-177215, etc.).

[0006]

The thermosetting or photocurable resin used in the first method and the photocurable resin used in the second method have a high refractive index in order to improve the efficiency as an optical component. The thing of is desirable. However, when the conventional resin material has a high refractive index, the viscosity of the resin is improved and the resin material tends to be further crystallized.

Further, the photocurable resin used in the second method is required to have adhesiveness with a transparent molded body, but conventional resin materials have poor adhesiveness, and optical parts cannot be produced well. When this was used under high temperature and high humidity, the transparent molded product and the photocurable resin cured product were sometimes separated from each other. An object of the present invention is to provide a resin material having a high refractive index and a low viscosity, and to obtain a high performance optical component which cannot be obtained by the conventional technique.

[0008]

A feature of the present invention is that an acrylic or methacrylic resin composition is used as a resin material, and the compound of the general formula (1) or the general formula (2) is added to the composition. ˜100% by weight.

[0009]

[Chemical 1]

[0010]

[Chemical 2]

[0011]

The compounds of formulas (1) and (2) are liquid substances having a low viscosity at room temperature, and are colorless and transparent, have a high refractive index and have a low water absorption. The acrylic group or methacrylic group present in the molecule is excellent in reactivity, and easily undergoes a polymerization reaction by heat or energy rays to produce a cured product.

The compound of formula (1) has an aromatic ring or a halogen atom in the molecule and relatively reduces the amount of water-absorbing ester bond, so that a high refractive index and a low water absorption are secured.
R ₂ of the compound of formula (1) may be in the ortho, meta or para position with respect to the CH bond attached to the aromatic ring of benzhydrol, but it disturbs the symmetry of the molecule and is in a liquid state even at low temperature. To achieve this, the ortho position and the meta position are followed well, followed by the para position.

The compound of the formula (2) has excellent reactivity because it has two acryl groups or methacryl groups in the molecule, and also has a high refractive index and a low water absorption rate because it has an aromatic ring in an effective concentration. In the compound of formula (2), the chemical bond connecting two aromatic rings may be in the ortho, meta, or para position with respect to the CH ₂ bond attached to each aromatic ring, but the symmetry of the molecule is disturbed. However, in order to obtain a liquid state even at a low temperature, the ortho position and the meta position are followed well, and then the para position.

Since the compounds of the formulas (1) and (2) have a property of swelling transparent moldings such as plastics to some extent, acrylic and methacrylic resins containing the compound of the formula (1) are transparent. The adhesiveness with the molded product is improved.

Examples of the transparent molded article having adhesiveness with the acrylic and methacrylic resin according to the present invention include:
There are the following:

Acrylic resins such as polymethylmethacrylate and polyethylmethacrylate, polystyrene, copolymers of methylmethacrylate and styrene, copolymers of styrene and acrylonitrile, copolymers of styrene and acrylonitrile, styrene and isoprene Copolymers of, polycarbonate, cellulose derivatives such as cellulose acetate, cellulose acetate butyrate,
PVC.

Of these, acrylic resins, copolymers of methyl methacrylate and styrene, polycarbonates, and cellulose derivatives are common.

The compounds of the formulas (1) and (2) are contained in the acrylic and methacrylic resins according to the present invention in an amount of 5 to 1
It is preferable that the content is 00 wt%. When the amount of the compound of the formula (1) and the formula (2) is 5% by weight or less, the above-mentioned features of the compound of the formula (1) and the formula (2) such as low viscosity, high refractive index and low water absorption cannot be exhibited.

In the acrylic and methacrylic resin composition according to the present invention, the material to be combined with the compounds of formula (1) and formula (2) has an acrylic group or a methacrylic group in the molecule, and a thermal polymerization initiator or There is no particular limitation as long as it is radically polymerized by a photopolymerization initiator, but the following are useful, for example.

Monofunctional monomers phenyl acrylate or methacrylate, benzyl acrylate or methacrylate, 2-phenoxyethyl acrylate or methacrylate, 2-phenoxypropyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, bornyl acrylate or methacrylate, isobornyl acrylate or methacrylate, Dicyclopentenyl acrylate or methacrylate, tricyclodecane acrylate or methacrylate, bifunctional monomer bisphenol A diglycidyl ether acrylate or methacrylate, bisphenol F diglycidyl ether acrylate or methacrylate, a compound of the following general formula (3),

[0021]

[Chemical 3]

Here, R ₁ , R ₃ , R ₄ : -H or -C
H ₃ n: integer of 1 to 4 Urethane acrylate or methacrylate compound represented by the general formula (4) or the general formula (5),

[0023]

[Chemical 4]

[0024]

[Chemical 5]

Here, R ₁ : -H or -CH ₃ R ₅ : -H or -CH ₃ or -C ₂ H ₅ R ₆ , R ₇ :

[0026]

[Chemical 6]

A urethane acrylate or methacrylate compound of the general formula (6),

[0028]

[Chemical 7]

Here, R ₁ : -H or -CH ₃ m: an integer of 1 to 4 neopentyl glycol acrylate or methacrylate, 1,6-hexanediol acrylate or methacrylate, 1,10-decanediol acrylate or methacrylate, Multifunctional monomers pentaerythritol tetraacrylate or methacrylate, dipentaerythritol hexaacrylate or methacrylate.

In the acrylic and methacrylic resin composition according to the present invention, the thermal polymerization initiator or photopolymerization initiator is particularly preferable as long as it produces a radical by heat or light to initiate radical polymerization of an acrylic group or a methacrylic group. Without limitation, the following are useful, for example:

Thermal polymerization initiators Peroxides such as benzoylperoxide, methylethylperoxide, t-butylperoxylaurate, cyclohexanoneperoxide, di-isopropylperoxycarbonate, ferrocene, cobalt naphthenate and the like. A combination of the organic metal salts of 1) as a reaction accelerator.

Photopolymerization Initiator Benzyl such as benzyl and methyl-o-benzoate, benzoin such as benzoin benzoin ethyl ether and benzoin isobutyl ether, benzophenone such as benzophenone and 4-methoxybenzophenone, acetophenone 2-2-getoxy Acetophenones such as acetophenone, 2-chlorothioxanthone,
Anthraquinones such as 2-methylthioxanthone, benzylmethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropane-1-
ON, etc., and these may be used alone or in combination of two or more.

[0033]

EXAMPLES Next, examples of the present invention will be described in detail. Example 1: Monofunctional compound A and bifunctional compound B were prepared as general acrylic and methacrylic compounds.

[0034]

[Chemical 8]

[0035]

[Chemical 9]

Further, the benzhydrol derivative and methacrylic acid were reacted to obtain the following methacrylic acid esters (compounds C, D and E of the formula 1).

[0037]

[Chemical 10]

To the general compound B, the general compound A and the compounds C, D and E according to the present invention are respectively added, and further the photopolymerization initiator 1- (4-isopropylphenyl) is added.
2-hydroxy-2-methylpropan-1-one 2
wt% was added. Each composition was a transparent liquid substance, and the viscosity at 25 ° C. was measured.

The composition was sandwiched between two glass plates having a thickness of 1 mm so that the composition had a thickness of 1 mm, and a high pressure mercury lamp (light intensity of 150 mW / c at a wavelength of 365 nm was used).
FIG. 3 shows the refractive index of each cured product measured at a wavelength of 589.3 nm after photo-curing (m ² , 30 seconds) and then leaving it at 120 ° C. for 1 h to perform post-curing.

When the compound (C, D, E) according to the present invention is added to the general compound (Compound B), the viscosity of the composition is lowered,
Moreover, the refractive index is improved. On the other hand, when a general acrylic compound monomer (compound A) is added to a general acrylic compound (compound B), the viscosity of the composition is lowered, but the refractive index is not improved.

Generally, workability is important when manufacturing an optical component in a resin casting or replica forming process. The fluidity of the resin is good, and the viscosity of the liquid that does not cause leakage from the mold material or entrain air bubbles is 50 to 1000 mPa · s.
Is appropriate. Also, to improve the efficiency of optical components,
The larger the refractive index, the more preferable, but it is often required that the refractive index is at least 1.57 or more.

From this point of view, as shown in FIG.
It can be seen that by adding the compound of formula 1 (C, D, E) to the general compound B, a material having preferable properties for optical parts can be obtained.

Example 2: 2,2'-biphenyldimethanol diacrylate was reacted with acrylic acid to prepare the following 2,2'-biphenyldimethanol diacrylate (compound F of formula 2).
Got

[0044]

[Chemical 11]

General compound A and compounds C, D and E according to the present invention are respectively added to compound F according to the present invention, and a photopolymerization initiator 1- (4-isopropylphenyl) -2-hydroxy is further added. -2-Methylpropane-1-
2 wt% of ON was added. Each composition was a transparent liquid substance, and the viscosity at 25 ° C. was measured.

The composition was sandwiched between two glass plates having a thickness of 1 mm so that the composition had a thickness of 1 mm, and a high pressure mercury lamp (light intensity of 150 mW / c at a wavelength of 365 nm was used).
FIG. 4 shows the refractive index of each cured product measured at a wavelength of 589.3 nm after photocuring (m ² for 30 seconds), leaving it at 120 ° C. for 1 h to perform postcuring.

For the compound F of the formula 2 according to the present invention, a general acrylic compound (compound A) and the compound 1 of the formula 1 according to the present invention are used.
When the compounds (C, D, E) of (1) are added, the viscosity of the resin composition decreases to 1000 mPa · s or less, and the refractive index is 1.
It is possible to realize a material having an improved property of 57 or more and having preferable characteristics for optical parts.

Example 3: Acrylic and methacrylic resins were mixed as shown in Table 1, and 2 g of 1-hydroxycyclohexyl phenyl ketone, a photopolymerization initiator, was added to and dissolved in 98 g of the resin. Each composition was a transparent liquid substance, and the viscosity at 25 ° C. was measured. This composition was sandwiched between two glass plates having a thickness of 1 mm so that the composition had a thickness of 1 mm, and a high pressure mercury lamp (light intensity 150 mW / cm ² , 30 at a wavelength of 365 nm was used).
After photo-curing for 2 sec., The mixture was left at 120 ° C. for 1 h for post-curing, and the refractive index of each cured product measured at a wavelength of 589.3 nm was measured. The general resins of Comparative Examples 1 to 3 had a problem that the viscosity was too large or the refractive index was too small. However, the compositions containing the compound of formula 1 according to the present invention,
As shown in Examples 1 to 13, the viscosity is 50 to 1000 mP.
It satisfies the target level of optical parts with a · s (25 ° C) and refractive index of 1.57 or more. The cured products of the compositions of Examples 1 to 13 all had a water absorption rate of 1 w after being left in water at 25 ° C for 1 week.
The value was within t%.

Example 4: Acrylic and methacrylic resins were mixed as shown in Table 2, and 2 g of the photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone was added to 98 g of the resin and dissolved. Each composition was a transparent liquid substance, and the viscosity at 25 ° C. was measured. This composition was sandwiched between two glass plates having a thickness of 1 mm so that the composition had a thickness of 1 mm, and a high pressure mercury lamp (light intensity 150 mW / cm ² , 30 at a wavelength of 365 nm was used).
After photo-curing for 2 sec., It was left for 1 h at 120 ° C. to perform post-curing, and the refractive index of each cured product measured at a wavelength of 589.3 nm was measured. The general resin of Comparative Example 4 had problems such as insufficient curing and a too small refractive index, but the composition containing the compound of Formula 1 or Formula 2 according to the present invention was 14 to 26, the viscosity is 50 to
The target level of optical parts is satisfied with 1000 mPa · s (25 ° C.) and a refractive index of 1.57 or more. In addition, Example 14-
The cured products of composition No. 25 each had a water absorption rate of 1 wt% or less after being left in water at 25 ° C. for 1 week.

Example 5: Resin composition 9 of Tables 1 and 2
To 9 g, 1 g of a thermal polymerization initiator, methyl ethyl ketone peroxide, was added and dissolved to form a composition having a thickness of 1 mm.
The composition was sandwiched between the two glass plates of 1 mm so as to have a thickness of 1 mm, and left at 70 ° C. for 1.5 hours + 110 ° C. for 2 hours to be heat-cured. The viscosity of the resin before curing and the refractive index after curing were measured, and almost the same results as in the lower row of Table 1 and the lower row of Table 2 were obtained.

[0051]

[Table 1]

[0052]

[Table 2]

Example 6: 50 wt% of each of the compounds C, D and E was added to the compound B of Example 1. Also,
50 wt% of each of the compounds A, C, D and E was added to the compound F of Example 2. 1- (4-
Seven kinds of photocurable resin compositions were prepared in which 2 wt% of isopropylphenyl) -2-hydroxy-2-methylpropan-1-one was added.

As illustrated in FIG. 1, 970x730x
Prepared in advance in the space (2) of the master mold (1a, 2b) in which the 10 mm quartz glass plate (1a) and the brass Fresnel pattern mold (2b) having the same area are arranged in parallel at an interval of 3 mm. The photocurable resin composition (4) was injected. Quartz glass (1a)
Resin mold injected from the side with a metal halide lamp (light intensity 100 mW / cm ² , 1 minute at a wavelength of 365 nm) is photo-cured, and a master mold consisting of a quartz glass plate (1a) and a mold (2b)
(1a, 2b) was removed to obtain a Fresnel plate as an optical component (5a) composed of a photocurable resin cured product (4). The plate was placed on a general glass plate with the Fresnel surface facing upward, and heat-treated at 80 ° C. for 1 hour.

Fresnel plates were manufactured using seven types of photocurable resins, and the warp per 100 mm width was
It was within 0.1 mm. Further, the surface of the Fresnel plate had a sawtooth-shaped cross section with a Fresnel pitch of 0.11 mm accurately transferred from the mother die.

This Fresnel plate has an input side focal point of 859 m.
The output side focus was 9800 mm when m was set, and the focus variation could be kept within 10% of the target.

As shown in FIG. 5, the luminous body (7) and the lens
A projection type television (11) consisting of (8), a mirror (9) and a screen (10) is prepared. Of the screen (10), a front plate (12) is prepared in advance, and a Fresnel plate is prepared.
As (13), the one previously prepared in this example was used. As a result of the operation test of the projection type television, it was found that the Fresnel plate according to the present invention can be sufficiently put to practical use, in which color shift and image distortion are not recognized, and this projection type television is 40 ° C. 95% RH. No abnormality was found in the image even after being left for 1000 hours.

Example 7: 50 wt% of each of the compounds C, D and E was added to the compound B of Example 1. Also,
50 wt% of each of the compounds A, C, D and E was added to the compound F of Example 2. 1- (4-
Seven kinds of photocurable resin compositions were prepared in which 2 wt% of isopropylphenyl) -2-hydroxy-2-methylpropan-1-one was added.

As illustrated in FIG. 2, 970x740x
A transparent molded product (3) made of a 3 mm methyl methacrylate-styrene copolymer and a master mold (1c) with a brass Fresnel pattern having the same area as this were prepared, and the master mold (1c) was kept at 40 ° C.
The previously prepared photocurable resin composition (4) is injected into the space (2) between the transparent molding (6) and the mother die (1c) to a thickness of about 200 μm, and then the transparent molding (6) ) Side, a high pressure mercury lamp (light intensity 50 mW / cm ² , 30 seconds at a wavelength of 365 nm)
Then, the resin composition (4) was photocured. When a force was applied between the transparent molded body (6) and the master mold (1c), the master mold (1c) and the photocurable resin cured product (4) were peeled off, and the transparent molded body (6) Optical component (5b) with photocurable resin cured product (4) attached on top
As a result, a Fresnel plate was obtained.

Fresnel plates were produced using seven types of photocurable resins, and the warp per 100 mm of plate width was
It was within 0.1 mm. Further, the surface of the Fresnel plate had a sawtooth-shaped cross section with a Fresnel pitch of 0.11 mm accurately transferred from the mother die.

This Fresnel plate has an input side focal point of 859 m.
The output side focus was 9800 mm when m was set, and it was possible to keep the focus variation within 5%, which is sufficiently within 10% of the target.

When this plate was used as a Fresnel plate of a projection type television screen as shown in FIG. 5,
It was found that no color misregistration or image distortion was observed, and that the projector could be used practically.
No abnormality was found in the image even after standing at 95 ° C RH for 1000 hours.

[0063]

As described above, according to the present invention, a material having colorless and transparent, low viscosity, high refractive index, and low water absorption has good workability during manufacturing and enables highly efficient optical parts. .

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram of an optical component according to the present invention,

FIG. 2 is a manufacturing process diagram of an optical component according to the present invention,

FIG. 3 is a diagram showing characteristics of a resin material according to the present invention,

FIG. 4 is a diagram showing characteristics of the resin material according to the present invention,

FIG. 5 is a diagram illustrating a projection television to which the Fresnel plate according to the present invention is applied.

[Explanation of symbols]

 1a, 1b ... Mother mold, 2 ... Space, 3 ... Injection port, 4 ... Resin material, 5a, 5b ... Optical part, 6 ... Transparent molded body, 7 ... Issuer, 8 ... Lens, 9 ... Mirror, 10 ... Screen , 11 ... Projection type television, 12 ... Front plate, 13 ... Fresnel plate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03B 21/62 7316-2K // B29K 33:04 105: 32 B29L 11:00 4F

Claims (7)

[Claims] 1. An acrylic and methacrylic resin composition is placed in a mother mold, the resin composition is cured by heat or energy rays, and then the resin composition and the mother mold are peeled off to form an optical component. In the present invention, an acrylic- and methacrylic-based resin composition contains the compound of the general formula (1) in an amount of 5 to 100% by weight. [Chemical 1] 2. An acrylic and methacrylic resin composition is placed in a mold, the resin composition is cured by heat or energy rays, and then the resin composition and the mold are peeled off to form an optical component. At this time, the optical component is characterized by containing 5 to 100% by weight of the compound of the general formula (2) in the acrylic and methacrylic resin composition. [Chemical 2] 3. An acrylic and methacrylic resin composition is placed in a mother mold, and after curing the resin composition by heat or energy rays, the resin composition and the mother mold are peeled off to form an optical component. According to the present invention, the optical component is characterized by containing 5 to 100% by weight of the compound of the general formula (1) and the compound of the general formula (2) in the acrylic and methacrylic resin composition. [Chemical 1] [Chemical 2] 4. An acrylic resin and a methacrylic resin composition are arranged between a transparent molding and a mother die having irregularities on the surface, and the resin composition is cured by heat or energy rays, and then the resin composition and In peeling off the matrix to form an optical component, the compound of the general formula (1) or the compound of the general formula (2) or the general formula (1) and the general formula ( An optical component containing 5 to 100% by weight of the compound of 2). [Chemical 1] [Chemical 2] 5. The optical component according to claim 1, 2, 3 or 4, wherein the optical component is an optical lens.
The optical components described. 6. The optical component according to claim 1, claim 2, claim 3, or claim 4, wherein the optical component is a Fresnel lens. 7. The optical component according to claim 1, 2, 3, or 4, wherein the optical component is a projection screen for television.