WO2014054547A1 - Resin composition, resin cured product, transparent composite, display-element substrate, and surface-light-source substrate - Google Patents

Description

Resin composition, cured resin, transparent composite, display element substrate and surface light source substrate

The present invention relates to a resin composition, a cured resin, a transparent composite, a display element substrate, and a surface light source substrate.
This application claims priority based on Japanese Patent Application No. 2012-219174 for which it applied to Japan on October 1, 2012, and uses the content here.

Epoxy compounds are widely used in industrial applications, electronic material applications, optical applications and the like from the viewpoints of heat resistance, moldability, transparency, and the like.

For example, Patent Documents 1 and 2 describe a cured resin obtained by curing an epoxy compound with an amine catalyst and imidazole.

However, all of these involve curing by heat. Generally, thermal energy is easy to diffuse and there is a lot of energy loss. Further, in a system in which a reaction is initiated by thermal energy, the pot life at normal temperature tends to be shortened. Therefore, a light energy curable resin composition that can give energy intensively and has a long pot life at room temperature is desired.

On the other hand, as a polymerization initiator of an epoxy compound, there is a cationic polymerization initiator. This is a photocation polymerization initiator that initiates the reaction by light energy such as ultraviolet light, and a thermal cationic polymerization initiator that initiates the reaction by heat. In particular, it reacts by applying light energy using a photocation polymerization initiator. In a system that starts the process, it is possible to concentrate energy.
However, in general, the polymerization reaction of a glycidyl type epoxy compound does not proceed with a cationic polymerization initiator, and a general alicyclic epoxy compound undergoes a polymerization reaction, but its reactivity is low.

Patent Document 1: Japanese Patent Application Laid-Open No. 2012-116979
Patent Document 2: JP 2012-158719 A

An object of the present invention is an epoxy compound-containing resin composition and an epoxy compound-containing resin composition that can obtain a cured resin, a transparent composite, a display element substrate, and a surface light source substrate with low energy. The object is to provide a cured product, a transparent composite, a display element substrate, and a surface light source substrate.

Such an object is achieved by the present invention described in the following [1] to [6].
[1] A resin composition having an epoxy compound (1), a cationic photopolymerization initiator, and a reaction accelerator, wherein the epoxy compound (1) is represented by the following (1A) and / or (1B) Is,
The reaction accelerator is an alicyclic epoxy compound (2) represented by the following (2):
A ratio of (1) and (2) is (1) :( 2) = 60: 40 to 99: 1.

（式（１Ａ）中のＲ_１は、任意の有機基を表す。ただし、（２）で示される構造は除く）

(R ₁ in the formula (1A) represents an arbitrary organic group, except for the structure represented by (2)).

（式（１Ｂ）中のＲ_２は、任意の有機基を表す）

(R ₂ in Formula (1B) represents an arbitrary organic group)

（式（２）中のＸは、－Ｏ－，－Ｓ－，－ＳＯ－，－ＳＯ_２－，－ＣＨ_２－，－ＣＨ（ＣＨ_３）－，－Ｃ（ＣＨ_３）_２－または単結合を表わす。）
［２］前記樹脂組成物が、積算光量５０～３０００ｍＪ／ｃｍ^２の光照射により硬化するものである
上記［１］に記載の樹脂組成物。
［３］前記エポキシ化合物（１）がビスフェノール型グリシジルエポキシ化合物、二以上の脂環式エポキシ構造を有する脂環式エポキシ化合物のいずれか１つ以上である上記［１］または［２］に記載の樹脂組成物。
［４］上記［１］ないし［３］いずれかに記載の樹脂組成物に光照射することで作製される、樹脂硬化物。
［５］上記［１］ないし［３］いずれかに記載の樹脂組成物と、ガラスフィラーを複合させ、光照射することで作製される、透明複合体。
［６］ガラスフィラーは、ガラスクロス、ガラス不織布のいずれかである、上記［５］に記載の透明複合体。
［７］全光線透過率が８０％以上である、上記［５］または［６］に記載の透明複合体。
［８］上記［４］または［５］に記載の樹脂硬化物または透明複合体を使用した、表示素子用基板。
［９］上記［４］または［５］に記載の樹脂硬化物または透明複合体を使用した、面光源用基板。

(X in the formula (2) is —O—, —S—, —SO—, —SO ₂ —, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — or Represents a bond.)
[2] The resin composition according to the above [1], wherein the resin composition is cured by light irradiation with an integrated light amount of 50 to 3000 mJ / cm ² .
[3] The above-mentioned [1] or [2], wherein the epoxy compound (1) is at least one of a bisphenol-type glycidyl epoxy compound and an alicyclic epoxy compound having two or more alicyclic epoxy structures. Resin composition.
[4] A cured resin product produced by irradiating the resin composition according to any one of [1] to [3] with light.
[5] A transparent composite produced by combining the resin composition according to any one of [1] to [3] above and a glass filler and irradiating with light.
[6] The transparent composite according to [5], wherein the glass filler is one of glass cloth and glass nonwoven fabric.
[7] The transparent composite according to [5] or [6], wherein the total light transmittance is 80% or more.
[8] A display element substrate using the cured resin or transparent composite according to the above [4] or [5].
[9] A surface light source substrate using the cured resin or transparent composite according to the above [4] or [5].

According to the present invention, a cured product can be obtained with low energy. In general, curing with a cationic polymerization initiator reduces the water absorption of the cured product because the number of hydroxyl groups decreases.

It is a figure which shows embodiment of the board | substrate for surface light sources of this invention. It is a figure which shows surface filler fixation with sectional drawing which shows embodiment of the board | substrate for surface light sources. It is sectional drawing which shows embodiment of a surface light source board | substrate, and is a figure which shows the preparation methods using a surface embossing type | mold.

(Resin composition)
The resin composition of this invention has the reaction accelerator which is an epoxy compound (1), a photocationic polymerization initiator, and an alicyclic epoxy compound (2). Each component will be described below.
(Epoxy compound (1))
Of the epoxy compound (1) used in the present invention, (1A) is an alicyclic epoxy compound having an epoxycyclohexane ring (however, the one having the structure shown in (2) is excluded). The reaction of the alicyclic epoxy compound represented by (1A) is initiated and proceeds by the photocationic polymerization initiator, but its reactivity is low when compared with the alicyclic epoxy compound shown in (2). However, the mixture of the alicyclic epoxy compound represented by (1A) and the alicyclic epoxy compound having the structure represented by (2) has a significantly improved reactivity compared to (1A) alone, The reaction by the photocationic polymerization initiator can proceed with energy. In addition, since the epoxy compound (1A) is highly flexible compared to (2), the copolymer of (1A) and (2) is more flexible than (2) a single polymer. Can be granted.

（式（１Ａ）中のＲ_１は、任意の有機基を表す。ただし、（２）で示される構造は除く）

(R ₁ in the formula (1A) represents an arbitrary organic group, except for the structure represented by (2)).

Examples of the epoxy compound represented by (1A) include, for example, an alicyclic epoxy and an alicyclic carbonyl type epoxy compound containing a carbonyl group, an alicyclic epoxy and an alicyclic ester type epoxy compound containing an ester bond, Examples include alicyclic carbonate type epoxy compounds containing cyclic epoxy and carbonate groups.
Among these, in order to impart heat resistance to the cured product after curing, an alicyclic epoxy compound having two or more alicyclic epoxy structures is desirable, and the alicyclic epoxy structure is particularly preferably an epoxycyclohexane ring. . Furthermore, it is more preferable that the epoxy group of the epoxycyclohexane is formed between adjacent carbons of cyclohexane. The bond to the epoxycyclohexane is preferably a structure that is carried out through carbon that is not adjacent to the carbon that forms the epoxy group. Specific examples include compounds having the following structure.

Moreover, (1B) is an epoxy compound which has a glycidyl type epoxy among the epoxy compounds (1) used by this invention, and is shown by the following structural formula. The reaction of the glycidyl type epoxy compound represented by (1B) generally does not start and proceed with the photocationic polymerization initiator. However, the mixture of the glycidyl-type epoxy compound represented by (1B) and the alicyclic epoxy compound having the structure represented by (2) has dramatically improved reactivity compared to (1B) alone, and has low energy. The reaction by the photocationic polymerization initiator can be advanced. In addition, since the epoxy compound (1B) is highly flexible as compared with (2), the copolymer of (1B) and (2) is more flexible than (2) a single polymer. Can be granted.

（式（１Ｂ）中のＲ_２は、任意の有機基を表す）

(R ₂ in Formula (1B) represents an arbitrary organic group)

Examples of the epoxy compound represented by (1B) include a glycidyl ether type epoxy compound containing a glycidyl group and an ether bond, a glycidyl ester type epoxy compound containing a glycidyl group and an ester bond, and a glycidyl amine type epoxy containing a glycidyl group and an amino group. Compounds and the like. Among these, as the glycidyl ether type epoxy compound, for example, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, biphenyl type, phenol novolac type, bisphenol A novolak type, glycidyl type having a fluorene skeleton, etc. Is used.
Among these, in order to give heat resistance etc. to the hardened | cured material after hardening, it is preferable to have two or more epoxy structures, and it is more preferable that it is a glycidyl type epoxy compound which has a benzene ring.
When the epoxy compound represented by (1B) is a glycidyl type epoxy compound having two or more glycidyl type epoxy structures and having a benzene ring, in addition to obtaining heat resistance of the cured product, Due to the high refractive index property, it becomes possible to produce a cured product having an adjusted refractive index as compared with (2) a cured resin product consisting of a single resin, and it is particularly suitable for optical applications such as display applications. Moreover, it becomes possible to use a glass filler with a high refractive index in combination by increasing the refractive index of the cured resin.

(Alicyclic epoxy compound (2))
As the alicyclic epoxy compound (2) used in the present invention, the alicyclic epoxy compound represented by the following (2) is used.

（式（２）中のＸは、－Ｏ－，－Ｓ－，－ＳＯ－，－ＳＯ_２－，－ＣＨ_２－，－ＣＨ（ＣＨ_３）－，－Ｃ（ＣＨ_３）_２－または単結合を表わす。）
（２）で示される脂環式エポキシ化合物は、単独でも光カチオン重合開始剤との反応性に優れるが、他の構造のエポキシ化合物と組み合わせた混合物も同様に光カチオン重合開始剤との反応性に優れる。
すなわち、（２）の構造の脂環式エポキシ化合物は、他の構造のエポキシ化合物の反応を促進する作用があると考えられる。
（２）で示す構造の脂環式エポキシ化合物については、Ｘが－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－または単結合であることが特に好ましい。

(X in the formula (2) is —O—, —S—, —SO—, —SO ₂ —, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — or Represents a bond.)
The alicyclic epoxy compound represented by (2) is excellent in reactivity with the photocationic polymerization initiator alone, but a mixture in combination with an epoxy compound having another structure is also reactive with the photocationic polymerization initiator. Excellent.
That is, the alicyclic epoxy compound having the structure (2) is considered to have an action of promoting the reaction of the epoxy compound having another structure.
In the alicyclic epoxy compound having the structure represented by (2), it is particularly preferable that X is —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — or a single bond.

The combination of (1) and (2) is not particularly limited. For example, (1A) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (product name of Daicel Corporation: “Celoxide 2021p”) , “Celoxide 2081”, “Epolide GT401”, “Epolide PB4700” (hereinafter, Daicel product name), or (1B) a glycidyl ether type epoxy compound containing a glycidyl group and an ether bond, a glycidyl group and Examples include glycidyl ester type epoxy compounds containing an ester bond, glycidyl amine type epoxy compounds containing a glycidyl group and an amino group, and particularly glycidyl ether type epoxy compounds such as bisphenol A type, bisphenol F type, hydrogenated bisphenol. (2) is (3,3 ′, 4,4′-diepoxy) bi, when it is a compound of a type such as diol A type, biphenyl type, phenol novolak type, bisphenol A novolak type, glycidyl type having a fluorene skeleton. Preferred is cyclohexyl or 2,2′-bis (3,4′-epoxycyclohexyl) propane, and when (1A) is 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Alternatively, when (1B) is a glycidyl ether-epoxy compound having a bisphenol A type, bisphenol F type, biphenyl type, phenol novolac type, or fluorene skeleton, (2) is (3, 3 ′, 4, 4 ′) More preferred is -diepoxy) bicyclohexyl.
Thereby, it becomes easy to aim at coexistence of characteristics, such as the above-mentioned flexibility improvement, high refractive index, heat resistance, and transparency.

The weight ratio of (1) and (2) is (1) :( 2) = 60: 40 to 99: 1. This makes it possible to improve the flexibility required for industrial applications, electronic material applications, and optical applications, and in particular, in optical applications, it is possible to widen the adjustment range of the refractive index.
The weight ratio of (1) to (2) is not particularly limited as long as it is within the range of (1) :( 2) = 60: 40 to 99: 1, but (1) :( 2) = 65: 35 to 99: 1 is preferable, and (1) :( 2) = 70: 30 to 90:10 is more preferable.
When the weight ratio of (1) and (2) is within the above range, it is possible to efficiently react the epoxy compound of (1) in which the reaction by the cationic polymerization initiator is difficult to proceed. Polymerization with can be performed. Furthermore, the characteristic (1) makes it possible to improve flexibility and / or widen the adjustment range of the refractive index in the same manner as described above.

(Photocationic polymerization initiator)
The resin composition of the present invention contains a photocationic polymerization initiator as a polymerization initiator. Such a cationic photopolymerization initiator reacts well with an epoxy compound having an epoxycyclohexane structure, and particularly has high reactivity with the alicyclic epoxy compound shown in (2), so that the resin composition of the present invention is concentrated. It is suitable for the process of applying light energy, and the pot life is extended.

Examples of the cationic photopolymerization initiator include onium salts such as a diazonium salt of Lewis acid, an iodonium salt of Lewis acid, and a sulfonium salt of Lewis acid. Specific examples of the cationic photopolymerization initiator include boron tetrafluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium Salts, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, and mixtures thereof. Specifically, Adekaoptomer SP-150, Adekaoptomer SP-170 manufactured by Adeka, Kayrad PCI-220, Kayalad PCI-620 manufactured by Nippon Kayaku, UVI-6990 manufactured by Union Carbide, CIT- manufactured by Nippon Soda 1370, CIT-1682, CIP-1866S, CIP-2048S, CIP-2064S, DPI-101 manufactured by Midori Chemical, DPI-102, DPI-103, DPI-105, MPI-103, MPI-105, BBI-101, BBI-102, BBI-103, BBI-105, TPS-101, TPS-102, TPS-103, TPS-105, MDS-103, MDS-105, DTS-102, DTS-103, and the like.

The resin composition of the present invention is cured with low energy, and can be cured even if the cumulative amount of light irradiated to the resin composition is reduced.
In order to cure the resin composition of the present invention, the integrated light quantity of necessary light, for example, preferably from 50 ~ 5000mJ / cm ^2, more preferably ^{100 ~ 4000mJ / cm 2, 150} ~ Even more preferably, it is 3000 mJ / cm ² .
Here, the light for measuring the integrated light amount is ultraviolet light, and the integrated light amount is an integrated light amount having a wavelength of 365 nm.
Further, “curing” means that many functional groups that can participate in the curing reaction are reacted in the resin composition. Specifically, the epoxy ring opening rate of the resin composition is 50% or more. It means that. What hardened | cured the resin composition is called resin cured material.

The epoxy ring opening rate is an index corresponding to the ring opening rate of epoxy groups in the resin composition.
As a method for measuring the epoxy ring-opening rate, first, an absorbance spectrum of a sample of the resin composition after the curing reaction is obtained by Fourier transform infrared spectroscopy (FT-IR).
Next, with respect to the obtained absorbance spectrum, the area of the peak derived from the epoxy group located near the wave number of 914 cm −1 was standardized by the area of the peak derived from the methylene group located near the wave number of 2900 cm −1. "Epoxy relative strength". Here, the ratio of the peak area derived from the epoxy group to the peak area derived from the methylene group is defined as the epoxy relative strength X of the sample, and the epoxy ring opening rate of the sample to be obtained is defined as Y (%).

In order to calculate the epoxy ring opening rate of the sample, the epoxy relative strength of the resin composition before curing is measured in advance. Since it is presumed that the epoxy group is not ring-opened in the resin composition before curing, this can be used as a standard sample. The epoxy relative strength of the resin composition before curing can be regarded as a strength corresponding to an epoxy ring-opening rate of 0%. The epoxy ring-opening rate Y (%) of the sample is calculated as a value obtained by multiplying 100 by the value obtained by dividing the epoxy relative strength X of the sample by the epoxy relative strength of the resin composition before curing. *

(Hardened resin, transparent composite and substrate for surface light source)
The resin cured product of the present invention is cured by mixing a resin composition containing each of the above components with various fillers as necessary and forming it into a desired shape, and applying heat energy and / or light energy. It is something to be made. In addition, the transparent composite of the present invention is obtained by mixing various fillers with the resin composition containing the above components and molding the resin composition into a plate shape and curing the resin composition. The substrate for a surface light source of the present invention is impregnated with a resin composition in which the above-mentioned components are mixed into glass fiber as a filler, and after being molded (shaped) into a plate shape in this state, the resin composition is cured. It has been made.

Since the cured resin, the transparent composite, and the surface light source substrate of the present invention have a reduced number of hydroxyl groups by curing with a cationic polymerization initiator as described above, the water absorption rate can be kept relatively low.
The water absorption rate of the cured resin, the transparent composite, and the surface light source substrate of the present invention is not particularly limited, but is preferably 0 to 5%, and more preferably 0 to 3%. In addition, the water absorption here refers to the water absorption after the resin cured product, transparent composite and / or surface light source substrate is dried at 50 ° C./24 hours and then immersed in pure water at 23 ° C. for 24 hours. Say.
When the water absorption rate of the cured resin, transparent composite and surface light source substrate of the present invention is within the above range, it is possible to suppress water absorption expansion, especially for industrial use, electronic material use and optical use that require dimensional accuracy. Is suitable.
Hereinafter, the filler will be described.

(Filler)
The cured resin, the transparent composite, and the surface light source substrate of the present invention may contain various fillers as necessary, and in this case, it is preferable to contain a glass filler. The glass filler is a filler (filler) composed of fibers or particles made of an inorganic glass material.

Examples of the glass filler include glass fiber including glass fiber cloth such as glass cloth and glass nonwoven fabric, glass chopped strands, glass beads, glass flakes, glass powder, and milled glass. In the transparent composite and the surface light source substrate, since the effect of reducing the linear expansion coefficient is high, glass fiber is preferably used, and glass fiber cloth is more preferably used. FIG. 1 illustrates a surface light source substrate 100 when the glass fiber 2 is a glass cloth. The glass fiber 2 shown in FIG. 1 is composed of a longitudinal glass yarn (warp) 2a and a transverse glass yarn (weft) 2b, and the longitudinal glass yarn 2a and the transverse glass yarn 2b are substantially orthogonal to each other. . Examples of the woven structure of the glass fiber 2 include a plain weave shown in FIG. 1, a nanako weave, a satin weave, and a twill weave. A plain weave is a woven structure in which warps and wefts are alternately woven. Nanako weaving is a woven structure in which a plurality of warp yarns and a plurality of weft yarns are alternately crossed. The satin weave is a woven structure woven so that one of warp and weft is extended to the surface. A twill weave is a weave structure in which warp or weft weaving continues diagonally.

Examples of the inorganic glass material include E glass, C glass, A glass, S glass, T glass, D glass, NE glass, quartz, low dielectric constant glass, and high dielectric constant glass. E glass, S glass, T glass, and NE glass, which are easy to obtain with few ionic impurities, are preferably used. In particular, from the viewpoint of obtaining a substrate having a low linear expansion, S glass or T glass having an average linear expansion coefficient of 5 ppm / K or less at 30 ° C. to 250 ° C. is more preferably used, and is easily available and inexpensive. From E, glass E is more preferably used.

The content of the glass filler is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and more preferably 10 to 80% by mass with respect to the cured resin, the transparent composite, and the cured resin in the surface light source substrate. The amount is preferably 30 to 70% by mass. If the content of the glass filler is within this range, it is easy to mold the resin cured product, the transparent composite, and the substrate for the surface light source, and the effect of reducing the linear expansion due to the composite of the resin composition and the glass filler is recognized. Moreover, if there is much glass filler amount, the uniformity of the resin amount per unit volume will improve, and the uniformity of stress will improve. When the resin amount and / or stress uniformity is improved, the undulation of the cured resin, the transparent composite, and the surface light source substrate is reduced. *

Moreover, it is preferable that the diameter which the fiber which comprises glass fiber and glass fiber cloth is 100 nm or less. Glass fibers and glass fiber fabrics that satisfy these conditions are less likely to scatter at the interface regardless of the difference between their refractive index and the refractive index of the epoxy compound, so that the cured resin, transparent composite, and surface light source The transparency of the substrate is relatively high.
In the surface light source substrate, the average diameter of the glass fibers is more preferably about 2 to 15 μm, further preferably about 3 to 12 μm, and most preferably about 3 to 10 μm. As a result, a surface light source substrate capable of achieving both high mechanical and optical characteristics and surface smoothness can be obtained. In addition, the average diameter of glass fiber is calculated | required as an average value of the diameter of 100 glass fibers measured from the observation image, observing the cross section of the board | substrate for surface light sources with various microscopes.

In addition, the cured resin, transparent composite and surface light source substrate of the present invention are thermoplastic or thermosetting resin oligomers and monomers, coupling agents, ultraviolet absorbers, as necessary, as long as the characteristics are not impaired. Agents, dyes, pigments, other fillers, etc. may be included.

The cured resin, the transparent composite and the surface light source substrate of the present invention can further increase the haze value by including a filler or the like in addition to the glass filler in the resin material. It becomes possible to make a substrate for a body and a surface light source.
When using a filler other than a glass filler, the refractive index difference between the filler other than the glass filler and the cured resin is preferably 0.01 or more and 3 or less. When this difference in refractive index is less than 0.01, there is a high possibility that a problem that the effect on light diffusibility is not sufficiently exhibited. On the other hand, there are very few materials having a difference in refractive index of 3 or more and lack selectivity.

Examples of materials used for fillers other than glass fillers include inorganic materials and mixtures thereof, such as zinc oxide, zirconium oxide, aluminum oxide, calcium oxide, titanium oxide, silica, and mixtures thereof. Examples of the organic material include those using acrylic, styrene, or a mixture thereof. Examples of the shape of the filler other than the glass filler include a spherical shape, a rod shape, a planar shape, and a fibrous shape.

The content of the filler other than the glass filler is preferably about 1 to 90 parts by mass and more preferably about 3 to 70 parts by mass with respect to 100 parts by mass of the glass filler.
In addition, when fillers other than a glass filler are particle | grains, it is preferable that the conversion particle size is 0.1 to 100 micrometer. When the thickness is 0.1 μm or less and 100 μm or more, there is a problem that the diffusion function cannot be sufficiently exhibited. When the filler is fibrous, the fiber diameter is preferably 0.1 μm or more and 100 μm or less. When the thickness is 0.1 μm or less and 100 μm or more, there is a problem that the diffusion function cannot be sufficiently exhibited.

(Cured resin)
Examples of the method for molding the resin composition include a method of casting into a mold. In particular, when forming into a plate shape (sheet shape), a method in which the resin composition is dissolved in a solvent and cast by a method such as gravure coating, spin coating, bar coating, dip coating or the like can be mentioned. Further, when a glass fiber cloth is used as the glass filler, a method of impregnating a component other than the glass filler from one or both sides of the glass fiber cloth to form a resin composition molded into a plate shape is used. Can be mentioned.

The curing of the resin composition is performed by irradiating the resin composition with light, that is, by irradiating with ultraviolet rays, electron beams, or the like in the present invention.

Further, after curing by the light irradiation, the reaction can be further advanced by performing a heat treatment as a secondary treatment.

The treatment temperature during the secondary treatment is preferably about 150 to 300 ° C., more preferably about 200 to 280 ° C. The treatment time is preferably about 0.1 to 5 hours, more preferably about 0.2 to 3 hours. Thereby, reaction can be advanced efficiently.

In addition, as a solvent which melt | dissolves a resin composition, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, ethyl acetate etc. are mentioned, for example.

The cured resin product of the present invention is preferably applied to, for example, lamp covers such as lighting fixtures and automobile lamps, optical lenses such as eyeglass lenses and camera lenses, and figurines.

(Transparent composite)
Further, the transparent composite of the present invention can be applied to various transparent substrates such as substrates for liquid crystal display devices, substrates for organic EL devices, substrates for color filters, substrates for electronic paper, substrates for solar cells, substrates for touch panels, etc. Preferably applied.

The average thickness of the transparent composite is not particularly limited, but is preferably about 10 to 300 μm, and more preferably about 20 to 200 μm.

(Substrate for surface light source)
The substrate for a surface light source of the present invention has a surface texture on which at least one surface of the substrate has irregularities, and the irregularities have an average roughness (Rz) of 10 points on the surface of 1 μm to 30 μm. It is.

The method of providing irregularities on the substrate surface is not particularly limited. For example, a method of fixing particles on the substrate surface, a method of mixing particles in a substrate and dispersing the particles near the substrate surface, a base substrate subjected to embossing, etc. Examples thereof include a method for forming and transferring a substrate, and a method for mechanically forming irregularities on the surface.

A method for providing irregularities on the substrate surface in the present invention will be described below.
First, a method for immobilizing particles on the substrate surface will be described.
The simplest and simplest method for providing irregularities on the substrate surface is to immobilize particles on the substrate surface. For example, a method in which a filler is dispersed in a solvent, applied to the substrate surface and dried to fix the filler on the substrate surface, a method in which the filler is applied to the substrate surface and then pressed and fixed, and an adhesive layer is provided on the substrate surface And a method of fixing the filler. FIG. 2 is a cross-sectional view of a surface light source substrate 100 in which a filler 4 is fixed on a composite layer including a resin 1 and glass fibers 2.

Next, a method of mixing particles in the substrate and dispersing the particles near the substrate surface will be described.
When producing the resin substrate, after mixing the particles with the resin composition before curing, the substrate can be produced and the surface can be provided with irregularities by the mixed particles.
Examples of the particles used here include a filler.

Furthermore, for the method of forming and transferring the substrate on the embossed mold, the method of transferring the embossed shape to the surface of the substrate with the embossed mold and the substrate on the embossed mold. There is a method in which after making and curing the substrate, it is removed from the mold and the unevenness of the mold is transferred.

There is also a method in which after the substrate is manufactured, the embossed mold is pressed to transfer the unevenness on the mold. In the case of this method, if the embossed mold is made of metal, the unevenness of the substrate surface can be produced with good reproducibility, which is suitable for mass production. In FIG. 3, the glass fiber 2 and the resin cured material 1 are further provided with a resin cured material layer 4, and an embossed base substrate 5, which is an embossed mold, is pressed against the resin cured material layer 4. The method for producing the unevenness for transferring the film was shown.

Further, as a method for mechanically producing irregularities on the surface, a method of directly roughing the substrate surface by sand blasting, a method of rubbing with a wire brush or sand paper, and mechanically imparting irregularities to the surface can be used.

The present invention will be described in more detail by way of examples, but this is merely an example, and the present invention is not limited thereby.

40 parts by weight of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (Celoxide 8000 manufactured by Daicel Corporation) having the following chemical formula (A) and a bisphenol type epoxy compound (Mitsubishi Chemical) having the following chemical formula (B) 60 parts by weight of jER828), 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) (ADEKA manufactured by ADEKA Corporation) (Optomer SP-170) A resin composition consisting of 1 part by weight was sandwiched between a PET film 100 μm (A4100 manufactured by Toyobo Co., Ltd.) together with a 1 mm spacer, and irradiated with metal halide UV light of about 300 mJ / cm ² from one side. . The PET film was peeled off to obtain a resin plate having a thickness of 1 mm. The resin composition was sufficiently cured and no tack was confirmed.

10 parts by weight of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (Celoxide 8000 manufactured by Daicel Corporation) and 90 parts by weight of a bisphenol type epoxy compound (jER828 manufactured by Mitsubishi Chemical Corporation), 4 as a photocationic polymerization initiator , 4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) (ADEKA OPTMER SP-170 manufactured by ADEKA Corporation) It was sandwiched with a PET film 100 μm (A4100 manufactured by Toyobo Co., Ltd.) together with a 1 mm spacer, and irradiated with metal halide UV light of about 950 mJ / cm ² from one side. The PET film was peeled off to obtain a resin plate having a thickness of 1 mm. The resin composition was sufficiently cured and no tack was confirmed.

30 parts by weight of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (Celoxide 8000 manufactured by Daicel Corporation) and 70 parts by weight of a phenol novolac type epoxy compound (jER152 manufactured by Mitsubishi Chemical Corporation), as a photocationic polymerization initiator 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) (ADEKA OPTMER SP-170 manufactured by ADEKA Corporation) 1 part by weight Was sandwiched with a PET film 100 μm (A4100 manufactured by Toyobo Co., Ltd.) together with a 1 mm spacer, and irradiated with metal halide UV light of about 300 mJ / cm ² from one side. The PET film was peeled off to obtain a resin plate having a thickness of 1 mm. The resin composition was sufficiently cured and no tack was confirmed.

10 parts by weight of (3,3 ′, 4,4′-diepoxy) bicyclohexyl (Celoxide 8000 manufactured by Daicel Corporation) and 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxy having the following chemical formula (D) 90 parts by weight of cyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corporation), 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) as a photocationic polymerization initiator (Adeka Co., Ltd., ADEKA Corporation SP-170) 1 part by weight of a resin composition is sandwiched with a 1 mm spacer between 100 μm PET films (A4100 manufactured by Toyobo), and a metal halide UV light of about 1000 mJ / cm ^{2 is applied} from one side. Irradiated. The PET film was peeled off to obtain a resin plate having a thickness of 1 mm. The resin composition was sufficiently cured and no tack was confirmed.

80 μm E glass-based glass cloth (Unitika Glass Fiber Co., Ltd. (# 2319 type) refractive index 1.555) (3, 3 ′, 4, 4′-diepoxy) bicyclohexyl (Celoxide 8000, manufactured by Daicel Corporation) 40 Parts by weight and 60 parts by weight of a bisphenol type epoxy compound (jER828 manufactured by Mitsubishi Chemical Corporation), 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexa as a photocationic polymerization initiator A resin composition consisting of 1 part by weight of fluoroantimonate) (ADEKA OPTMER SP-170 manufactured by ADEKA Corporation) was impregnated in vacuum for 2 hours and defoamed. The cloth impregnated with this resin composition was sandwiched between 100 μm PET films (A4100 manufactured by Toyobo Co., Ltd.), and cured by irradiation with metal halide UV light of about 300 mJ / cm ² from one side. Further, the PET film was peeled off, and the cured product was heated in a vacuum oven at 250 ° C. for 1 h to obtain an 80 μm transparent sheet.
Various physical properties of this composite transparent sheet are shown below.
Total light transmittance 90%
Haze: 3.8%
Average linear expansion coefficient (CTE): 12ppm / K (30-230 ° C) @MD
14ppm / K (30-230 ℃) @TD

The physical properties were measured by the following methods.
(A) Total light transmittance, haze Based on JIS-K-7361, the total light transmittance of the composite material was measured using a haze meter NDH: 2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
(B) Average linear expansion coefficient (CTE)
Using a TMA / S S 120 C type thermal stress strain measuring device manufactured by Seiko Instruments Inc., the temperature is raised from 30 ° C. to 230 ° C. at a rate of 5 ° C. per minute and held for 20 minutes. Thereafter, the average linear expansion coefficient was determined by measuring the value when cooled to 230 ° C. to 30 ° C. at a rate of 5 ° C. per minute. The measurement was performed in a tensile mode with a load of 5 g.

[Comparative Example 1]
100 parts by weight of a bisphenol type epoxy compound (Mitsubishi Chemical Corporation jER828), 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) as a photopolymerization initiator (Adeka Optomer SP-170 manufactured by ADEKA Co., Ltd.) A resin composition consisting of 1 part by weight is sandwiched between 100 μm PET films (A4100 manufactured by Toyobo Co., Ltd.) and irradiated with metal halide UV light of about 5000 mJ / cm ² from one side. did. When the PET film was peeled off, the resin composition remained fluid and was not sufficiently cured and a resin plate could not be obtained.

[Comparative Example 2]
100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corporation), 4,4′-bis [bis ((β-hydroxyethoxy) as a photocationic polymerization initiator ) Phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate) (adekatopomer SP-170 manufactured by ADEKA Corporation) and 1 part by weight of the resin composition are sandwiched between 100 μm PET films (A4100 manufactured by Toyobo Co., Ltd.) Then, a metal halide UV light of about 5000 mJ / cm ² was irradiated from one side. When the PET film was peeled off, the resin composition remained fluid and was not sufficiently cured and a resin plate could not be obtained.

According to the present invention, a resin produced from an epoxy compound-containing resin composition and an epoxy compound-containing resin composition capable of obtaining a cured resin, a transparent composite, a display element substrate, and a surface light source substrate with low energy. A cured product, a transparent composite, a display element substrate, and a surface light source substrate can be obtained. Therefore, the present invention can be suitably used for “a resin composition, a cured resin, a transparent composite, a display element substrate, and a surface light source substrate”, and is extremely important industrially.

1 Resin cured product 2a Glass fiber, longitudinal glass yarn (warp)
2b Glass fiber, transverse glass yarn (weft)
3 Filler 4 Hardened resin layer 5 Embossed base substrate 100 Surface light source substrate

Claims (9)

A resin composition having an epoxy compound (1), a cationic photopolymerization initiator, and a reaction accelerator, wherein the epoxy compound (1) is represented by the following (1A) and / or (1B) below. ,
The reaction accelerator is an alicyclic epoxy compound (2) represented by the following (2):
A ratio of (1) and (2) is (1) :( 2) = 60: 40 to 99: 1.

(R ₁ in the formula (1A) represents an arbitrary organic group, except for the structure represented by (2)).

(R ₂ in Formula (1B) represents an arbitrary organic group)

(X in the formula (2) is —O—, —S—, —SO—, —SO ₂ —, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₂ ) ₃ — or Represents a bond.) The resin composition according to claim 1, wherein the resin composition is cured by light irradiation with an integrated light amount of 50 to 3000 mJ / cm ² . The resin composition according to claim 1 or 2, wherein the epoxy compound (1) is one or more of a bisphenol-type glycidyl epoxy compound and an alicyclic epoxy compound having two or more alicyclic epoxy structures. A cured resin product produced by irradiating the resin composition according to any one of claims 1 to 3 with light. A transparent composite produced by combining the resin composition according to any one of claims 1 to 3 and a glass filler and irradiating with light. The transparent composite according to claim 5, wherein the glass filler is one of glass cloth and glass nonwoven fabric. The transparent composite according to claim 5 or 6, wherein the total light transmittance is 80% or more. A display element substrate using the cured resin or transparent composite according to claim 4. A surface light source substrate using the resin cured product or transparent composite according to claim 4.

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