TWI499599B - Curable resin composition and cured - Google Patents

Description

Curable resin composition and cured product thereof

The present invention relates to an optical property, heat resistance, and processability which are excellent in low color dispersion, high light transmittance, and the like, and optical properties, low water absorption, and inorganic materials under severe practical conditions such as moist heat conditions. A cured resin composition having improved adhesion and a cured product thereof.

Many monomers having reactive unsaturated bonds are cleaved by unsaturated bonds, and a polymer can be formed by selecting a catalyst in which a chain reaction occurs and appropriate reaction conditions. In general, since the kind of the monomer having an unsaturated bond is extremely diverse, the richness of the type of the obtained resin is also remarkable. However, a monomer having a high molecular weight molecular weight of 10,000 or more which is generally referred to as a polymer compound is relatively small. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkylstyrene, alkoxystyrene, norbornene, various acrylates, butadiene, cyclopentadiene, dicyclopentane Alkene, isoprene, maleic anhydride, maleic imide, fumarate, allyl compound and the like are representative monomers. A wide variety of resins can be synthesized by copolymerizing these monomers individually or by these.

The use of these resins is mainly limited to the field of relatively inexpensive livelihood machines, and is hardly applicable to the field of advanced technology requiring high heat resistance, dimensional stability or micro-machining in the field of optical materials. The reason for this is that the polymer which is usually synthesized from the above-mentioned monomers is thermoplastic, and in order to satisfy the mechanical properties, a large number of high molecular weight bodies are required, so that the properties required in the field of advanced technology such as heat resistance and fine workability are exhibited.

On the other hand, the curable resin composition is suitably used as, for example, a mechanical part material, an electric appliance, an electronic part material, an automobile part material, a civil construction material, a molding material, and the like, and can also be used as a material for a coating or an adhesive. In addition, when it is combined with an inorganic base material to form a mixed member, not only the coefficient of thermal expansion is lowered, but also the refractive index of the inorganic substance and the resin can be adjusted, and the appearance of the resin composition and the cured product thereof can be controlled, and transparency can be exhibited. It is therefore particularly suitable as a material in electrical and electronic parts or in optical applications. For example, the digital camera module is being mounted on a mobile phone and the like, and is being miniaturized, and is also required to be reduced in cost. Furthermore, the demand for a car camera for a novel use or a bar code reader for a home buyer is increased. When it is used for such applications, it is required to have not only heat resistance of the soldering at the time of manufacture, but also high-temperature exposure in the summer in actual use, and high reliability such as long-term heat resistance and low water absorption.

As a method for solving the disadvantages of such a vinyl-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth)methacryloyl group or a vinyl ether group in a pendant. For example, Patent Document 1 discloses a (meth)methacryl fluorenyl side group-type polymer obtained by cationically polymerizing a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) and photopolymerization. A photosensitive composition formed by an initiator. Further, Patent Document 2 discloses a photosensitive composition comprising a (meth)methacryloyl group-based polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. Further, Patent Document 3 discloses a carboxylic acid ester solvent in which a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) or the like has an inactive photoreactive unsaturated group in cationic polymerization. Among the compounds, a cationic polymerization catalyst is used, and homopolymerization or copolymerization is carried out to obtain a method for producing a polymer solution.

However, according to the technique of using a heterogeneous polymerizable monomer disclosed in these documents, when the produced reactive polymer is used, a low water absorption property which is required in the field of advanced optical lenses and erbium is not obtained, A polymer and a curable resin composition having improved properties such as moldability, heat resistance, and high transparency, and optical properties under excellent practical use conditions such as damp heat conditions, and adhesion to inorganic materials.

On the other hand, Patent Document 4 discloses that a monovinyl aromatic compound and a bifunctional (meth) acrylate are copolymerized, and have a reactivity derived from a bifunctional (meth) acrylate in a side chain (methyl group). A soluble polyfunctional vinyl aromatic copolymer of structural units of acrylate groups. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in this document has excellent heat decomposition resistance to high temperature heat warp, and has a reactive (meth) acrylate group in a side chain, and is processability. It is excellent in solvent solubility, but it cannot be used in optical lenses for low-color dispersion applications. It is limited in practical use and is a material that does not improve adhesion to inorganic materials.

Further, Patent Document 5 discloses a composition characterized in that it contains 1 to 25% by weight of a linear aliphatic divalent alcohol having 4 to 8 carbon atoms in a methyl methacrylate (MMA) slurry. The bis(meth) acrylate is used as a constituent component. Further, it is disclosed that the MMA-based slurry composition disclosed in the literature is produced by using MMA, or MMA, and a vinyl copolymer copolymerizable therewith, a chain transfer agent in the presence of a polymerization initiator, in an inert gas (for example). In a N ₂ gas atmosphere, room temperature or heat polymerization is carried out. Moreover, as a specific example of the chain transfer agent in this document, only sulfur compounds such as lauryl mercaptan, octyl thioglycolate, toluene thiol, naphthol, benzyl mercaptan, etc., regarding 2, 4-di Phenyl-4-methyl-1-pentene (hereinafter also referred to as DMP) is not specifically disclosed. Further, it is not suggested that the refraction at the time of moist heat can be multiplied by coexisting with a structural unit containing a monofunctional (meth) acrylate (a) having a terminal group derived from DMP and an alicyclic structure of an alicyclic structure. The rate of disagreement occurred. Moreover, the composition obtained by the technique disclosed in this document does not improve the adhesion to inorganic materials under severe practical use conditions such as damp heat conditions.

Further, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di(meth)acrylate compound, and also discloses the use of DMP, but the amount thereof is used as a decimal point of a usual chain transfer agent. It is used in a few percent, since the product is also a cross-linked gelator and does not exhibit solvent solubility.

Further, Patent Document 7 discloses a thermosetting resin composition for a color filter, which comprises a self-curable copolymer and an organic solvent, and the self-curable copolymer contains (1) an epoxy group-containing compound. A constituent unit composed of (meth) acrylate, (2) hydroxyl group-containing (meth) acrylate, (3) (meth) acrylic acid, and (4) aromatic group-containing (meth) acrylate. Moreover, the self-hardening copolymer obtained by the technique disclosed in the literature can be used to obtain a desired molecular weight range in the polymerization stage, and mercaptopropionic acid, mercaptopropionate, thioglycol, thioglycerol, twelve can be used. A well-known molecular weight modifier such as a thiol or an α-methylstyrene dimer. However, in the technique disclosed in this document, since no bifunctional or more vinyl compound having a plurality of vinyl groups is added at the time of polymerization, only one or less end derived from a molecular weight modifier can be introduced into the polymer chain. The function of having a function from the terminal group gives the disadvantage of insufficient formation.

Further, in this document, the self-curable copolymer obtained by the disclosed technique forms a thermosetting resin composition in a resin composition with an epoxy resin, but with the acrylate resin, The hardening reaction does not occur, and there is a disadvantage that the strength and heat resistance of the resin composition to be blended are lowered.

Therefore, it has excellent optical characteristics such as low color dispersion and high light transmittance, and has a balance of characteristics such as low water absorption, moldability, and heat resistance, and optical characteristics under low practical conditions such as damp heat conditions. A curable resin composition having improved water absorbability, heat resistance, and adhesion to an inorganic material has not been present.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 49-13212

[Patent Document 2] Japanese Patent Publication No. 51-34433

[Patent Document 3] Japanese Patent Publication No. 54-27394

[Patent Document 4] JP-A-2008-247978

[Patent Document 5] JP-A-57-167340

[Patent Document 6] JP-A-2002-121228

[Patent Document 7] Special Opening 2009-1770 Bulletin

An object of the present invention is to provide a curable resin composition which has excellent optical characteristics such as low color dispersion and high light transmittance, and is an optical lens in an advanced technical field such as low water absorption, workability, and heat resistance. The various properties required for the material are excellently balanced, and the optical properties and adhesion to the inorganic material under severe practical conditions such as hot and humid conditions are improved.

The present invention relates to a curable resin composition which is a resin composition containing (A) component and (B) component as essential components,

(A) component: a monofunctional (meth) acrylate (a) having an alicyclic structure, a monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group, and a bifunctional (meth) acrylate (c) a copolymer obtained by copolymerization with a component of 2,4-diphenyl-4-methyl-1-pentene (d), and having a bifunctional (meth) acrylate in a side chain ( a reactive (meth) acrylate group of c) having a copolymer of structural units derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal, and having a weight average molecular weight of 2,000 ～ 50000, more soluble in soluble polyfunctional (meth) acrylate copolymer of toluene, xylene, tetrahydrofuran, dichloroethane or chloroform;

(B) component: a monomer having one or more functional groups having a polymerizable unsaturated double bond;

The blending amount of the component (A) is from 1 to 70% by weight based on the total of the components (A) and (B), and the blending amount of the component (B) is from 99 to 30% by weight.

The amount of introduction of 2,4-diphenyl-4-methyl-1-pentene (d) in the component (A) is represented by a molar fraction M _d represented by the following formula (1), preferably The amount of the reactive (meth) acrylate group derived from the bifunctional (meth) acrylate (c) to the side chain is 0.02 to 0.35, and the molar fraction M _c1 represented by the following formula (2) It is preferably 0.05 to 0.5.

Further, the amount of introduction of the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group in the component (A) is represented by a molar fraction M _b represented by the following formula (3), preferably 0.05. to 0.60, and having an alicyclic structure of a monofunctional (meth) acrylate introduction amount (a), the molar fraction as shown in (4) represented by the following formula M _a, preferably from 0.05 to 0.60.

M _d = (d) / [(a) + (b) + (c) + (d)] (1)

M _c1 =(c1)/[(a)+(b)+(c)] (2)

M _b = (b) / [(a) + (b) + (c)] (3)

M _a = (a) / [(a) + (b) + (c)] (4)

Here, (a), (b), (c), and (d) represent a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, and a monofunctional group derived from an alcoholic hydroxyl group ( a structural unit of methyl acrylate (b), a structural unit derived from a bifunctional (meth) acrylate (c), and 2,4-diphenyl-4-methyl-1-pentene (d) The number of moles of the structural unit. Further, (c1) represents the number of moles of the structural unit containing a bifunctional (meth) acrylate group in the side chain.

The monofunctional (meth) acrylate (a) having an alicyclic structure is preferably selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, and cyclohexyl acrylate. , dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and One or more monofunctional (meth) acrylates having an alicyclic structure in the group formed by dicyclopentyl acrylate.

The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is preferably selected from the group consisting of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and partially ethoxylated. A monofunctional (meth) acrylate in a group of 2-hydroxy methacrylate.

The bifunctional (meth) acrylate (c) is preferably selected from the group consisting of 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol. One or more bifunctional (meth) acrylates in the group of diacrylate and dimethylol tricyclodecane diacrylate.

The monomer or oligomer having one or more functional groups having a polymerizable unsaturated double bond as the component B is preferably a monofunctional (meth) acrylate having an alicyclic structure and 2 More than one (meth) acrylate selected from functional (meth) acrylates.

The curable resin composition of the present invention preferably further contains a photopolymerization initiator as the component (C).

Moreover, the present invention is a cured product obtained by curing the curable resin composition. Furthermore, the present invention is an optical material characterized by being formed of the above-mentioned cured product. As the optical material, an optical plastic lens or a crucible is preferable.

According to the present invention, it is possible to provide a curable resin composition having excellent optical characteristics such as low color dispersion and high light transmittance, and an optical lens in an advanced technical field such as low water absorption, workability, and heat resistance. The various properties required for the material are excellently balanced, and the optical properties and adhesion to the inorganic material under severe practical conditions such as hot and humid conditions are improved.

[Formation of the Invention]

Hereinafter, the curable resin composition of the present invention will be described in detail.

The soluble polyfunctional (meth) acrylate copolymer (hereinafter also referred to as a copolymer) of the component (A) of the present invention contains a monofunctional (meth) acrylate (a) having an alicyclic structure and has an alcohol Hydroxy-terminated monofunctional (meth) acrylate (b) with bifunctional (meth) acrylate (c) monomer, and 2,4-diphenyl-4-methyl-1-pentene (d a copolymer obtained by copolymerization and having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain, and having 2, 4 at the end a soluble polyfunctional (meth) acrylate copolymer of t-phenyl-4-methyl-1-pentene (d). Here, the so-called solubility means that it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The soluble test was carried out under the conditions shown in the synthesis examples. Further, it is understood that the monofunctional (meth) acrylate means that the number of ethylenic double bonds present in the molecule is one, and the bifunctional (meth) acrylate means that the number of ethylenic double bonds present in the molecule is Two, polyfunctional (meth) acrylate copolymers mean that the number of ethylenic double bonds present in a molecule is two or more. Further, a monofunctional (meth) acrylate having an alicyclic structure (a) is also referred to as a component (a), and a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b) is also referred to as a component (b). The bifunctional (meth) acrylate (c) is also referred to as component (c), and the 2,4-diphenyl-4-methyl-1-pentene (d) is also referred to as component (d) or DMP.

Since the copolymer is obtained by copolymerizing a monofunctional (meth) acrylate and a bifunctional (meth) acrylate, it has a branched structure or a crosslinked structure, but the amount of the structure is limited to exhibit solubility. degree. Therefore, it is a copolymer having a structural unit (c1) containing an unreacted (meth)acrylic group derived from a bifunctional (meth)acrylate (c) in a side chain. This unreacted (meth)acrylic group is referred to as a pendant (meth)acrylic group, and since it exhibits polymerizability, it can be polymerized by further polymerization treatment, and a solvent-insoluble resin cured product is given.

Further, the copolymer has a structural unit derived from the component (d) at the terminal. By introducing this structural unit at the end of the copolymer, it is possible to obtain a cured product having improved moldability such as mold release property.

The copolymer has a structural unit derived from the component (a), a unit derived from the component (b), a structural unit derived from the component (c), and a structural unit derived from the component (d). Here, in the structural unit derived from the component (c), both of the polymerizable double bonds (referred to as vinyl groups) contained in the two (meth) acrylates are involved in polymerization to form a branched structure or a cross. The structural unit (c2) of the unit structure is an unreacted (meth)acrylic group structural unit (c1) which contains only one vinyl group to participate in polymerization and which does not react with other vinyl groups. The DMP of the component (d) has a chain transfer agent and prevents the increase in molecular weight and is present at the end of the copolymer.

The amount of the component (d) to be introduced into the copolymer is 0.02 to 0.35, preferably 0.03 to 0.30, and particularly preferably 0.05 to 0.15, expressed by the molar fraction M _d represented by the following formula (1).

M _d = (d) / [(a) + (b) + (c) + (d)] (1)

Here, (a), (b), (c), and (d) show the number of moles of the structural unit of each component from (a), (b), (c), and (d). By introducing a structural unit derived from the component (d) in the above range at the end of the copolymer, mold release property and low water absorbability can be improved.

The bifunctional (meth) acrylate (c) causes branching or crosslinking of the copolymer, and at the same time, produces a pendant vinyl group, imparts curability to the copolymer, and exhibits heat resistance upon hardening, thereby achieving importance as a crosslinking component. task.

As the bifunctional (meth) acrylate, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclohexane can be used. Decane dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol II a bifunctional (meth) acrylate such as acrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, hexanediol dimethacrylate or diethylene glycol dimethacrylate, However, it is not subject to these restrictions.

As a suitable specific example of the bifunctional (meth) acrylate, cyclohexane dimethanol diacrylate and dihydroxyl group are preferably used from the viewpoints of cost, ease of polymerization control, and heat resistance of the obtained polymer. Tricyclodecane diacrylate.

The copolymer has a structural unit (c1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain, but a structural unit (c1) represented by the formula (2) The molar fraction M _c1 may be 0.05 or more and 0.5 or less, preferably 0.1 to 0.3.

Mc ₁ = (c1) / [(a) + (b) + (c)] (2).

Here, (c1) in the formula represents the number of moles of the structural unit (c1) containing a (meth) acrylate group. By satisfying the above molar fraction, it is possible to obtain a molded article which is excellent in light or heat hardenability and excellent in heat resistance and mechanical properties after curing.

The structural unit derived from the bifunctional (meth) acrylate (c) may contain a structural unit (c1) and other structural units, but is derived from a structure containing all of the bifunctional (meth) acrylate (c) The molar fraction M _{c of the} unit (c) may be from 0.1 to 0.7, preferably from 0.15 to 0.65.

M _c = (c1) / [(a) + (b) + (c)] (5).

In order to improve the solvent solubility, low water absorption, heat resistance, optical properties, and processability of the copolymer, a monofunctional (meth) acrylate (a) having an alicyclic structure is important. As such a monofunctional (meth) acrylate having an alicyclic structure, it is selected from isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, and bicycloacrylate. Pentene ester, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentyl methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure in the group formed by the ester are not limited thereto. By introducing the structural unit derived from these components into the copolymer having an alicyclic structure, not only the gelation of the polymer can be prevented, the solubility in the solvent can be improved, and the low color dispersion of the copolymer can be improved. Optical properties such as properties, low water absorption, and heat resistance.

The monofunctional (meth) acrylate (a) having an alicyclic structure is preferably a compound represented by the following formula (a1).

A-R-C-(R’)n (a1)

Here, A is a (meth) propylene fluorenyloxy group, R is a single bond or an alkylene group having a carbon number of 1 to 10 or a polyalkylene oxide group, a C-based aliphatic ring, and an R' group is substituted by an aliphatic ring. An alkyl group having 1 to 10 carbon atoms, and n is 0 to 5.

As another preferable monofunctional (meth)acrylate (a) which has an alicyclic structure, the compound represented by following formula (a2) is mentioned.

【化1】

Here, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having an alicyclic structure having 6 to 15 carbon atoms, R ³ represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer of 0 to 10.

As a specific specific example, from the viewpoints of cost, prevention of gelation, and moldability of the obtained polymer, it is selected from isobornyl methacrylate, isobornyl acrylate, and cyclohexyl methacrylate. , cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure in the group of ethyl ester and dicyclopentanyl methacrylate.

The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is important in order to improve the adhesion to the inorganic material under severe practical use conditions of the copolymer under moist heat conditions. Examples of such a monofunctional (meth) acrylate having an alcoholic hydroxyl group include 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and 3-hydroxypropyl (meth)acrylate. 4-hydroxybutyl methacrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and partially ethoxylated 2-hydroxy methacrylate, preferably 2-hydroxyethyl methacrylate. The (meth) acrylate system having such an alcoholic hydroxyl group may be used singly or in combination of two or more kinds.

The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is preferably a compound represented by the following formula (b1).

[Chemical 2]

Here, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrocarbon group having one hydroxyl group having 2 to 6 carbon atoms.

a monofunctional (meth) acrylate (b) containing an alcoholic hydroxyl group, a molar fraction of (a) component, (b) component, and (c) component in the copolymer, and a monofunctional group derived from an alcoholic hydroxyl group The molar fraction of the structural unit of the (meth) acrylate (c) may be 0.05 or more and 0.60 or less, and preferably 0.1 to 0.3, in terms of Mb represented by the formula (3).

M _b = (b) / [(a) + (b) + (c)] (3).

Here, (a), (b), and (c) in the formula represent the number of moles of the structural unit of each component from (a), (b), and (c). By satisfying the above molar fraction, it is possible to obtain a copolymer which is excellent in the optical properties under severe practical use conditions such as damp heat conditions and in good adhesion to inorganic materials.

Further, M _a represented by the above formula (4) represents 0.05 or more and 0.60 or less, preferably 0.1 to 0.3.

DMP has a function as a chain transfer agent to control the molecular weight of the copolymer. The molecular weight of the copolymer is represented by a weight average molecular weight Mw, and is in the range of 2,000 to 50,000, preferably in the range of 3,000 to 25,000. Further, the range of Mw of 6,000 to 50,000 is good for the relationship with the component (B). The formability and mold release property of the cured resin are improved by using a relatively low molecular weight copolymer.

Further, as the component (e) for the purpose of improving solvent solubility and processability of the copolymer, a monofunctional (meth) acrylate having no alicyclic structure and a hydroxyl group may be added. Examples of such (meth) acrylate include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, and 2-ethyl acrylate. The hexyl hexyl ester, octyl acrylate or the like is preferably methyl methacrylate or n-butyl acrylate. These (meth) acrylate type single systems may be used singly or in combination of two or more kinds, but are preferably selected from the group consisting of methyl methacrylate, methyl acrylate and n-butyl acrylate. (meth) acrylate.

Further, these other structural units derived from the monomer component (e) are related to the structural unit derived from the monomer component (a), the structural unit derived from the monomer component (b), and the structure derived from the monomer component (c). The total amount of units can be less than 30% of the range.

Further, from another viewpoint, the soluble polyfunctional (meth) acrylate copolymer may contain 20 to 55 mol% of the structural unit derived from the component (a) and 20 to 35 mol of the structural unit derived from the component (b). %, the structural unit derived from the component (c) is 55 to 10 mol%, preferably 50 to 12 mol%, more preferably 40 to 15 mol%, and the structural unit derived from the component (d) is 2 to 35 mol. ear%. When the structural unit derived from the bifunctional (meth) acrylate (c) is less than 10 mol%, the heat resistance of the cured product is insufficient, and if the structural unit exceeds 55 mol%, the moldability is lowered. The strength of the formed article is significantly lowered.

Further, the other structural unit derived from the monomer (e) component may be in a range of less than 30 mol% with respect to the total amount of the structural unit derived from the component (a) and the structural unit derived from the component (b).

The method for producing the copolymer used as the component (A) is not particularly limited, and DMP, two kinds of monofunctional acrylate aromatic compounds, and bifunctional (meth) acrylate are adjusted to a desired content, as needed. The polymerization is carried out by polymerization at a temperature of 20 to 200 ° C using a radical polymerization initiator and a solvent, and is recovered by a method generally used, for example, by a stripping method in the precipitation of a weak solvent.

This copolymer had a solubility of 1 g or more dissolved in 100 g of the above solvent. It is preferred to dissolve 5 g or more of 100 g of the above solvent at 25 °C.

Next, the component (B) will be explained.

As the component (B), a monomer having one or more functional groups having a polymerizable unsaturated double bond is used. Here, the monomer as the component (B) may be an oligomer, but is not the same as the copolymer of the component (A). Further, the term "different" means that it does not contain a monofunctional (meth) acrylate having an alicyclic structure (a), a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), or a bifunctional group. A copolymer obtained by copolymerizing a component of (meth) acrylate (c) and 2,4-diphenyl-4-methyl-1-pentene (d). Further, the oligomer may be a homopolymer or a copolymer, and may be a low molecular weight polymer having a molecular weight (Mw) of 10,000 or less, preferably 6,000 or less, more preferably 5,000 or less, and still more preferably 1,000 or less. . Further, the monomer as the component (B) may be a compound having no molecular weight distribution, and in this case, a plurality of compounds may be used. A monomer having a molecular weight of 1,000 or less is preferred. When the monomer is an oligomer, the above molecular weight means Mw. Further, in the relationship with the component (A), the relationship between the molecular weight Mw of the monomer of the component (B) and the Mw of the copolymer of the component (A) may be lower than that of the component (A), and more preferably 1,000 or less.

The above-mentioned single system has one or more functional groups having a polymerizable unsaturated double bond, and examples of the functional group having a polymerizable unsaturated double bond include a vinyl group and a (meth)methacryloyl group.

The monomer as the component (B) is preferably a (meth) acrylate monomer. When the (meth) acrylate single system has one or more (meth) methacryl fluorenyl groups in the molecule, one type or two or more types may be used. The (meth) acrylate used as the component (B) can be used in combination with the component (A) without lowering the curability, and the viscosity of the composition can be adjusted, and the heat resistance can be multiplied and simultaneously improved. Optical properties such as low color dispersion and high light transmittance. Further, physical properties such as hardness and flexibility of the cured product can be improved.

The (meth) acrylate single system may have a molecular weight of 6,000 or less, preferably 5,000 or less, and particularly preferably 1,000 or less. Further, it may be a monomer (oligomer) having a molecular weight distribution such as polyethylene glycol di(meth)acrylate, and the Mw at this time may be 6,000 or less, preferably 5,000 or less, more preferably 2,000 or less. , especially good for 1000 or less. Advantageously, a monomer or a mixture thereof formed from a compound having no molecular weight distribution.

The (meth) acrylate monomer may be a copolymerizable with the component (A). For example, it is preferably a (meth) acrylate having an alicyclic structure, and particularly preferably a monofunctional, bifunctional or trisole. A functional (meth) acrylate, more preferably a monofunctional (meth) acrylate. Further, the (meth) acrylate monomer as the component B is preferably an aliphatic acrylate of C4 to 20, and may have one to three unsaturated bonds derived from an acrylate. The (meth) acrylate having an alicyclic structure is excellent in compatibility with the component (A), and is effectively multiplied by the component (A) to improve the low water absorption, heat resistance, and optical properties of the entire composition. Processability. Further, the urethane-modified (meth) acrylate or the ethylene oxide-modified (meth) acrylate has an effect of improving the softness of the cured product. Further, in order to improve the hardness of the cured product, a trifunctional or higher (meth) acrylate single system is effective.

Examples of the (meth) acrylate monomer include acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy (meth) acrylate. Butyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrogen (meth) acrylate Oxime ester, phenoxyethyl (meth)acrylate, phenyl polyethoxylate (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, o-phenyl (meth)acrylate Phenolic monoethoxylate, o-phenylphenol poly(ethoxy) (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) Tribromophenoxyethyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1,4-butane Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylic acid Ester, bisphenol A polyethoxy di(meth) acrylate (for example, SR manufactured by Sartomer) -349, SR-348, etc.), bisphenol A polypropoxy di(meth) acrylate, bisphenol F polyethoxy di(meth) acrylate, ethylene glycol di(meth) acrylate, Trimethylolpropane triethoxyethyl methacrylate, tris(2-hydroxyethyl)isocyanate tri(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (a) Acrylate, polyethylene glycol di(meth)acrylate (for example, SR-344, SR-268, manufactured by Sartomer Co., Ltd.), tris(propylene decyloxyethyl)isocyanate, pentaerythritol IV (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxy trimethyl Di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol di(meth)acrylate and hydroxytrimethylacetic acid neopentyl glycol (for example, manufactured by Nippon Kayaku Co., Ltd.) KAYARAD HX-220, HX-620, etc.), trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate, ditrimethylolpropane tetra(a) base A monomer such as an acrylate or a urethane-modified (meth) acrylate (for example, EBACRYL 8405, EBACRYL 8402, manufactured by Daicel Scientific Co., Ltd.). Particularly preferred are 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, Pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, urethane modified (meth) acrylate, bisphenol A polyethoxy di(meth) acrylate, ethylene Alcohol di(meth)acrylate.

The curable resin composition of the present invention may contain a polymerization initiator as the component (C), and is preferably a photopolymerization initiator. The curable resin composition of the present invention can be molded and cured by thermal polymerization. However, when an optical material such as a lens is molded and cured, photocuring which is controlled by a strict shape is advantageous. Therefore, it is preferred to add a photopolymerization initiator. .

Examples of the photopolymerization initiator of the component (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether. Affinity; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichlorobenzene Ketone, 2-hydroxyl is 2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio) Acetophenones such as phenyl]-2-morpholinylpropan-1-one; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-pentyl hydrazine Anthraquinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; acetophenone dimethyl ketal, benzyl a ketal such as dimethyl ketal; a diphenyl ketone, a 4-benzylidene-4'-methyldiphenyl sulfide, or a 4,4'-bismethylaminodiphenyl ketone; Diphenyl ketone; 2,4,6-trimethyl benzhydryl diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc. Phosphine oxides and the like.

These may be used singly or in combination of two or more kinds, and may be a tertiary amine such as triethanolamine or methyldiethanolamine, ethyl N,N-dimethylaminobenzoate or N,N-dimethyl. An accelerator or the like of a benzoic acid derivative such as isoamyl benzoate is used in combination.

The curable resin composition of the present invention contains the above-mentioned (A) component and (B) component as essential components, and the content ratio thereof is as follows. The blending amount of the component (B) is 99 to 30 parts by weight, preferably 90 to 30 parts by weight, more preferably 100 parts by weight based on 100 parts by total of the blending amount of the component (A) and the component (B). It is 60 to 45 parts by weight. In addition, when the component (C) is contained, the blending amount of the component (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the blending amount of the component (B) and the component (A). Preferably it is 1.0 to 5 parts by weight.

From another viewpoint, each of the curable resin composition may contain (A) component: 1 to 69% by weight, (B) component: 30 to 98% by weight, and (C) component: 0.1 to 10% by weight. More preferably, it is (A) component: 25-60 weight%, (B) component: 39-74 weight%, and (C) component: 1-5 weight%. When the blending ratio of the component (A), the component (B) and the component (C) is within the above range, the moldability and the heat resistance and the heat resistance and the heat resistance are improved. Balance of characteristics of optical properties. Further, when the amount of the component (C) is too small, the curing is likely to be insufficient, and the heat resistance and the light resistance are lowered. When the amount is too large, the mechanical strength is lowered and the heat resistance is lowered. Further, when the organic solvent and the filler are contained in the curable resin composition, the above content is calculated by excluding the above.

Further, in the curable resin composition of the present invention, a polymerization inhibitor, an antioxidant, a mold release agent, a photosensitizer, an organic solvent, a decane coupling agent may be added to the curable resin composition of the present invention as needed. , leveling agent, antifoaming agent, antistatic agent, and UV absorber, light stabilizer, inorganic, organic fillers, anti-fungal agents, antibacterial agents, etc., and give their respective functions.

The curable resin composition of the present invention can be obtained by mixing the above components (A), (B) and (C), and optionally other components in an arbitrary order. The curable resin composition of the present invention is stable over time.

The curable resin composition of the present invention can be obtained by irradiating an active energy ray such as ultraviolet rays. Here, when the active energy ray is irradiated and hardened, examples of the light source to be used include a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet light, a high-pressure mercury lamp for photocopying, a medium-pressure mercury lamp, a high-pressure mercury lamp, and super. High-pressure mercury lamps, electrodeless lamps, metal halide lamps, or electron beams of scanning type, curtain type electron beam acceleration paths. Moreover, when the curable resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet rays required for curing can be about 300 to 20,000 mJ/cm ² . Further, in order to sufficiently cure the resin composition, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert gas atmosphere such as nitrogen.

Further, the curable resin composition of the present invention may be used in combination with a decane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoaming agent, a photostabilizer, an antioxidant, a plasticizer, an antistatic agent, and a filling. Additives such as agents and solvents.

The cured product of the curable resin composition of the present invention can be obtained by irradiating an active energy ray such as an ultraviolet ray or a visible light laser according to a usual method. When ultraviolet rays are used, they are irradiated with a low pressure or high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. In particular, as the light source, a lamp having a high energy intensity of 350 to 450 nm is preferred.

The refractive index of the cured product of the curable resin composition of the present invention obtained by irradiating an active energy ray such as ultraviolet rays is preferably 1.49 or more at 25 ° C, and more preferably 1.51 or more at 25 ° C. In particular, when a bismuth lens sheet is produced from the resin composition for an optical material of the present invention, if the refractive index of the cured product is less than 1.49 at 25 ° C, there is a problem that sufficient front luminance cannot be ensured.

Further, the Abbe number of the cured product (a value inherent to a substance which defines the property of changing the refractive index due to the wavelength of light) is preferably 40.0 or more, and more preferably 50.0 or more. If the Abbe number of the cured product is less than 40.0, it is not preferable because the chromatic aberration is large and color bleeding occurs.

The cured resin obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material such as a ruthenium or a lens. It is particularly suitable as a material for an optical plastic lens such as a bismuth lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens, or an aspherical lens. Moreover, such a lens system can be advantageously used in an image pickup apparatus. Further, the curable resin composition or the cured resin may be used in a photoelectron-oriented application such as an optical disk, an optical fiber, or an optical waveguide, a printing ink, a paint, a clear paint, a lacquer, or a hard coat.

Moreover, the cured product of the curable resin composition of the present invention can also be used as an adhesive layer, and as an article having such an adhesive layer, for example, a mobile phone, a portable game machine, a digital camera, or the like can be used.

When the polarizing film and the protective sheet are bonded to each other by using the curable resin composition of the present invention, for example, it is not limited to a protective sheet made of an alkali-free glass or quartz glass which is excellent in active energy ray permeability, and even a large absorbing ultraviolet ray is used. A protective sheet such as a force plate or a polycarbonate can be used because of the good reaction hardenability of the composition.

The curable resin composition of the present invention can be formed by using a coating device such as a roll coater, a spin coater or a screen printing method on a substrate such as a polarizing film, and the film thickness of the adhesive is 1 to 100 μm. The method is applied, and the protective sheet is attached, and ultraviolet rays are irradiated from above the protective sheet to be hardened, and then applied.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto. Furthermore, the parts in each case are all parts by weight. Further, the measurement of each physical property in the examples was carried out by sample preparation and measurement by the method described below.

(1) Molecular weight and molecular weight distribution of polymers

The molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylate copolymer was determined by using GPC (manufactured by Tosoh Corporation, HLC-8120GPC) in a solvent: tetrahydrofuran (THF), a flow rate: 1.0 ml/min, and a column temperature: 40 °C. The molecular weight of the copolymer was measured using a calibration curve of monodisperse polystyrene as a molecular weight in terms of polystyrene.

(2) Structure of the polymer

It was determined by 13 C-NMR and 1H-NMR analysis and elemental analysis using a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL. Using chloroform-d1 as a solvent, a resonance line of tetramethylnonane was used as an internal standard.

(3) Soluble test

To 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane, and chloroform) at 25 ° C, 1 g of a copolymer was added, and the mixture was stirred for 30 minutes using a magnetic stirrer, and the solubility was visually confirmed. All of the above organic solvents were dissolved, and no solubility was observed when the gel was formed: ○.

(4) Preparation of test piece for physical property measurement

A gap of 0.2 to 1.0 mm is opened between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, and a curable composition is injected into the glass mold which is wound around the outer periphery by a polyimide film, and the glass mold is injected therefrom. On the other hand, after irradiating the ultraviolet rays with the high-pressure mercury lamp for 5 seconds, the glass mold was placed in an inert gas oven under a nitrogen stream, and hardened by heating at 180 ° C for 1 hour. The hardened resin sheet was released from the glass mold and used for various physical properties.

(5) Determination of refractive index

The refractive index and Abbe number at 589 nm were measured with an Abbe refractometer (manufactured by ATAGO Co., Ltd.).

(6) Hue (YI); a plate having a thickness of 1.0 mm was measured with a color difference meter (MODEL TC-8600 manufactured by Tokyo Electron Co., Ltd.), and its YI value was shown.

(7) Haze (turbidity) and total light transmittance

A 0.2 mm thick sample was prepared, and the haze (turbidity) and total light transmittance of the sample were measured using an integrating sphere type light transmittance measuring apparatus (SZ-Σ90 manufactured by Nippon Denshoku Co., Ltd.).

(8) Mold release property: It was evaluated by the ease of releasing the hardened resin from the mold.

○‧‧‧‧Good mold release from the mold

△‧‧‧‧Demolition is slightly difficult

×‧‧‧‧Difficulty in demoulding or mold residue

(9) Mold reproducibility: The surface shape of the hardened resin layer and the surface shape of the mold were observed.

○‧‧‧‧Reproducible

△‧‧‧‧The conditions of hardening (light, heat) are reproducible

×‧‧‧‧Reproducible

(10) Burr, Leakage: When the hardened resin was released from the mold, the size of the burrs generated outside the product portion of the molded article and the degree to which the resin leaked into the gap of the mold were evaluated.

○‧‧‧‧ The amount of burrs generated was less than 0.05 mm, and the leakage of resin into the mold gap was less than 1.0 mm.

△‧‧‧‧ The amount of burrs generated is 0.05mm or more and less than 0.2mm. The resin leaked into the mold gap system of 1.0 mm or more and less than 3.0 mm.

×‧‧‧‧ The amount of burrs generated is 0.2 mm or more, and the leakage of resin into the die gap is 3.0 mm or more.

(11) Reflow heat resistance: A 1 mm-thick flat plate was used as a sample, and a spectral transmittance of 400 nm was measured by a spectrophotometer CM-3700d (manufactured by Konica-Minolta Co., Ltd.). The measurement time was after the heat resistance test after post-cure for 60 minutes at 180 ° C and after the heat resistance test at 260 ° C for 8 minutes in an air oven.

(12) Water absorption rate

A 1 mm thick flat plate was used as a sample, and the weight of the sample dried under vacuum at 60 ° C for 24 hours was taken as Wo, and it was weighed to a scale of ±0.1 mg, at a temperature of 85 ° C and relative humidity. : 1 week of humidification in a constant temperature and humidity chamber of 85%. After humidification, the moisture adhering to the sample was blown off, and the sample was weighed to a scale of ±0.1 mg to obtain W. The water absorption rate was calculated by the following formula. Three identical samples were prepared and tested in the same manner.

Wo/W×100=water absorption rate

(13) Heat cycle resistance

Using a 157 mW ultra-high pressure mercury lamp, the sample of the alkali-free glass (thickness: 0.7 mm) and the 2 mm-thick acrylic plate with a thickness of 25 μm was used at 1 cycle, -35 ° C for 30 minutes, 85 MPa at an energy of 3000 mJ. After 100 cycles of the conditions of 30 minutes, the peeling appearance of the two substrates was observed, and the peeling evaluation was ○, and the peeling evaluation was ×.

(14) Moisture resistance

Using a 157 mW ultra-high pressure mercury lamp, with an energy of 3000 mJ, a sample of a thickness of 25 μm for an alkali-free glass (thickness; 0.7 mm) and a 2 mm thick acrylic plate was observed, and 100 at 60 ° C, 90% RH was observed. The peeling appearance of the two substrates after the hour was evaluated as ○ without peeling and × as peeling evaluation.

(15) Peel strength

An alkali-free glass (thickness: 0.7 mm) having a width of 25 mm and a length of 50 mm and a 2 mm thick acrylic plate were bonded so as to have a resin thickness of 25 μm, and an ultrahigh pressure mercury lamp of 157 mW was used to have an energy of 3000 mJ. Harden. For this test piece, the tensile strength at the time of the test at a rate of 5 mm/min was measured using a tensile tester.

(Measurement of physical properties of sheet-like cured product and test sample)

The test samples of the sheet or the film-like cured product were produced by the methods described in Examples 21 to 32. The test method of the flaky cured product is shown below.

(16) Pencil hardness

The pencil hardness of the film was measured in accordance with JIS K 5400 using a pencil scratch tester. Specifically, on a PET film having a hard coat layer (thickness: 15 μm), a pencil was applied with a load of 1 kg from an angle of 45 degrees, and scratched by about 5 mm to confirm the damage. Five measurements were performed, and the pencil hardness at the first level where the damage was observed twice or more in five times was described as the pencil hardness test result.

(17) Scratch resistance test

A load of 200 g/cm ² was applied to the steel wool # 0000, and the load was reciprocated 200 times, and the state of the damage was confirmed using a stereoscopic microscope, and it was judged by comparison with the sample of the 5-stage limit. Evaluation of 5 means no damage, evaluation of 1 means that damage occurred, and evaluation of 4 to 2 means that the degree of damage was in the middle.

(18) Adhesion

According to JIS K 5400, slits of 11 vertical and horizontal are introduced at intervals of 1 mm on the surface of the film to make 100 checkerboards. It is the number of squares remaining without peeling off when the celluloid tape is attached to the surface.

(19) Bending

The applied sheet was formed by bending the UV coated surface to the outside and bending it to 180 degrees.

A: There is no abnormality in appearance and it is bent.

B: Cracking or peeling occurred on the surface of the coating film.

C: Cracking occurred in each substrate.

(20) Transparent perception

After coating and hardening on the substrate, in order to determine the transparency of the film, it is determined by a state in which the visibility is blurred or the like.

A: I get a very transparent feeling, B: I have a sense of transparency, C: I am confused.

Synthesis Example 1

Dimethylol tricyclodecane diacrylate 3.2 mol (926.5 ml), isobornyl methacrylate 8.0 mol (1814.1 ml), 2-hydroxypropyl methacrylate 4.8 mol (645.5 ml), 2,4-Diphenyl-4-methyl-1-pentene 4.8 mol (1145.9 ml) and 2400 ml of toluene were placed in a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to make the reaction 6 hour. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer A1392.6 g (yield: 40.5 wt%).

The obtained copolymer A had Mw of 8,950, Mn of 3,470, and Mw/Mn of 2.58. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer A contained a total of 18.2 mol% of a structural unit derived from dimethyloltricyclodecane diacrylate, and a total of 51.1 mol%. The structural unit derived from isobornyl methacrylate, 30.7 mol% of a structural unit derived from 2-hydroxypropyl methacrylate. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is based on dimethyloltricyclodecane diacrylate, isobornyl methacrylate, 2- The total amount of hydroxypropyl methacrylate and 2,4-diphenyl-4-methyl-1-pentene was present at 8.3 mol%. Further, the ratio of the pendant acrylate was 12.10 mol%.

The copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer A was a film which was transparent without being turbid.

Synthesis Example 2

1,4-butanediol diacrylate 4.8 mol (950.4 g), dicyclopentanyl methacrylate 6.4 mol (922.7 g), 2-hydroxypropyl methacrylate 4.8 mol (692.2 g), 2,4-Diphenyl-4-methyl-1-pentene 4.8 mol (1135 g) and 2400 ml of toluene were placed in a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to allow a reaction for 6 hours. . After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, separated by filtration, dried, and weighed to obtain a copolymer B.

The obtained copolymer B had Mw of 12,500, Mn of 3,640, and Mw/Mn of 3.43. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer B contained a total of 27.8 mol% of a structural unit derived from 1,4-butanediol diacrylate, and a total of 27.8 mol% derived from The structural unit of dicyclopentanyl methacrylate, 41.6 mol% of the structural unit derived from 2-hydroxypropyl methacrylate. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is based on 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, and methyl group. The total amount of 2-hydroxypropyl acrylate and 2,4-diphenyl-4-methyl-1-pentene was present at 10.1 mol%. Further, the ratio of the pendant acrylate was 20.4 mol%.

The copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer B was a film which was transparent without turbidity.

Synthesis Example 3

1,4-butanediol diacrylate 5 mol (990 g), dicyclopentanyl methacrylate 1 mol (144.2 g), 2-hydroxypropyl methacrylate 4 mol (576.8 g), 2 4-Diphenyl-4-methyl-1-pentene 5 mol (1182 g) and 2400 ml of toluene were placed in a reactor of 10.0 L, and 240 mmol of benzoyl peroxide was added at 90 ° C to carry out a reaction for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, separated by filtration, dried, and weighed to obtain a copolymer C.

The obtained copolymer C had Mw of 9230, Mn of 3210, and Mw/Mn of 2.88. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer C contained a total of 45.6 mol% of a structural unit derived from 1,4-butanediol diacrylate, and a total of 12.3 mol% derived from The structural unit of dicyclopentanyl methacrylate, 42.1 mol% of the structural unit derived from 2-hydroxypropyl methacrylate. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is based on 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, and methyl group. The total amount of 2-hydroxypropyl acrylate and 2,4-diphenyl-4-methyl-1-pentene was present at 14.6 mol%. Further, the ratio of the pendant acrylate was 32.6 mol%.

The copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer C was a film which was transparent without being turbid.

Synthesis Examples 4 to 15 and Synthesis Examples 16 to 20

Various copolymers were synthesized by the same method as in Synthesis Example 1, and the types and amounts of acrylates were changed by blending as shown in Tables 1 and 2. Further, Synthesis Examples 16 to 20 are comparative examples for comparison. The results are summarized in Tables 1-2.

Examples 1 to 20 and Comparative Examples 1 to 8

The various copolymers synthesized in the synthesis examples and the additives such as (meth) acrylates and polymerization initiators were mixed at a ratio shown in Tables 3 and 4 to obtain a curable composition. Next, the curable resin composition was cured by the above various test methods to evaluate the performance. The performance evaluation results are shown in Tables 3 and 4.

Examples 21 to 26 and Comparative Examples 9 and 10

The components shown in Table 5 were blended (numbers are parts by weight) to obtain a curable resin composition as a hard coating material. Next, the curable resin composition was applied to a sheet of untreated polycarbonate (made of Mitsubishi Engineering Plastics: Iupilon Sheet NF-2000, sheet thickness: 1.00 mm) using a spin coater, and the coated surface was subjected to coating. After the release-treated PET protective film (thickness: 38 μm) was bonded, ultraviolet rays were irradiated with a high-pressure mercury lamp of 120 W/cm in an air atmosphere at a distance of 10 cm to obtain a sheet having a hard coat layer (thickness: 10 to 15 μm). Next, the performance of the hard coat layer (hardened product) was evaluated by the above various test methods. The combined performance evaluation results are shown in Table 5.

Examples 27 to 32 and Comparative Examples 11 and 12

The components shown in Table 6 were blended (numbers are parts by weight) to obtain a curable resin composition as a transparent coating material. Next, the curable resin composition was applied to a sheet of untreated polycarbonate (made of Mitsubishi Engineering Plastics: Iupilon Sheet NF-2000, sheet thickness: 1.00 mm) using a spin coater, and the coated surface was subjected to coating. After the release-treated PET protective film (thickness: 38 μm) was bonded, ultraviolet rays were irradiated with a high-pressure mercury lamp of 120 W/cm in an air atmosphere at a distance of 10 cm to obtain a sheet having a clear coat layer (thickness: 10 to 15 μm). Next, the performance of the clear coat (cured material) was evaluated by the above various test methods. The results of the combined performance evaluation are shown in Table 6.

Description of the tokens in the table

IBOMA: Isobornyl Methacrylate

DCPM: Dicyclopentyl Methacrylate

DCPA: Dicyclopentyl acrylate

HOP: 2-hydroxypropyl methacrylate

HO: 2-hydroxyethyl methacrylate

CD570: Ethoxylated 2-hydroxyethyl methacrylate

DMTCD: Dimethylol tricyclodecane diacrylate

14BDDA: 1,4-butanediol diacrylate

MMA: Methyl methacrylate

DCP-A: Tricyclodecane dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

1.9ND: 1,9-nonanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

FA-513M: Dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)

FA-513AS: Dicyclopentyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)

TMP: Trimethylolpropane trimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

TMP-A: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

AO-60: Adekastub AO-60 (made by Adeka Co., Ltd.: antioxidant)

Perbutyl O: tert-butylperoxy-2-ethylhexanoate (manufactured by Nippon Oil & Fats Co., Ltd.)

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, (manufactured by Ciba Specialty Chemicals Co., Ltd.)

SR-833S: Tricyclodecane dimethanol diacrylate (manufactured by Sartomer Co., Ltd.)

SR-349: EO modified bisphenol A diacrylate (manufactured by Sartomer Co., Ltd.)

SR-348: EO modified bisphenol A dimethacrylate (manufactured by Sartomer Co., Ltd.)

EBECRYL 8405: Ethyl urethane acrylate / 1,6-hexanediol diacrylate = 80/20 (Daicel Scientific Co., Ltd.)

EBECRYL 8402: urethane acrylate (Daicel Scientific Co., Ltd.)

DPHA: dipentaerythritol hexaacrylate (Daicel Scientific Co., Ltd.)

SR-285: tetrahydrofurfuryl acrylate (manufactured by Sartomer Co., Ltd.)

PhEA: phenoxyethyl acrylate

Irgacure 819: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation)

In Tables 1 and 2, the numbers of components (a) to (c) indicate the amount of use (mole), the number of moles in the digital acrylates in parentheses, and the number of DMP indicates the amount of use (mole), brackets The numbers in the numbers represent the % of moles relative to the total amount of acrylates. Further, when MMA is used as the other monomer component, this is calculated as an acrylate. Further, the content of each component is derived from the existence ratio (mol%) of the structural unit of each component present in the copolymer, and is calculated by the above formulas (1) to (5). Further, when MMA is used as the other monomer component, this is calculated as a structural unit derived from an acrylate.

Claims (16)

A curable resin composition which is a resin composition containing (A) component and (B) component as essential components, and (A) component: a monofunctional (meth)acrylate having an alicyclic structure (a) ), a monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group, a bifunctional (meth) acrylate (c) and 2,4-diphenyl-4-methyl-1-pentene (d) a copolymer obtained by copolymerization of a component having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain and having 2,4-diphenyl at the terminal The copolymer of the structural unit of 4-methyl-1-pentene (d) has a weight average molecular weight of 2,000 to 50,000, and is more soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Functional (meth) acrylate copolymer; (B) component: a monomer having one or more functional groups having a polymerizable unsaturated double bond; and a total of (A) component and (B) component, The blending amount of the component (A) is 1 to 50% by weight, and the blending amount of the component (B) is 99 to 50% by weight. The curable resin composition of claim 1, wherein the component (A) is a copolymer having a weight average molecular weight (Mw _A ) of 6000 to 50,000, and the component (B) is a (meth)acrylic acid having a molecular weight of 6000 or less. Ester monomer. The curable resin composition of the first aspect of the invention, wherein the component (B) has a monomer having one or more functional groups having a polymerizable unsaturated double bond and having a molecular weight of 1,000 or less. The curable resin composition of the first aspect of the invention, wherein the blending amount of the component (A) is 10 to 70% by weight based on the total of the components (A) and (B), and the component (B) The blending amount is 90 to 30% by weight. The curable resin composition of claim 1, wherein the amount of introduction of 2,4-diphenyl-4-methyl-1-pentene (d) in the component (A) is represented by the following formula ( 1) The molar fraction M _d shown is a soluble polyfunctional (meth) acrylate copolymer of 0.02 to 0.35; M _d = (d) / [(a) + (b) + (c) + (d)] (1) Here, (a), (b), (c), and (d) represent structural units derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, and have a structural unit of an alcoholic hydroxyl group of a monofunctional (meth) acrylate (b), a structural unit derived from a bifunctional (meth) acrylate (c), and a 2,4-diphenyl-4-methyl group The number of moles of the structural unit of 1-pentene (d). The curable resin composition of the first aspect of the invention, wherein the amount of the reactive (meth) acrylate group derived from the bifunctional (meth) acrylate (c) in the component (A) to the side chain is , expressed by the Mohr fraction M _c1 represented by the following formula (2), being 0.05 to 0.5; M _c1 = (c1) / [(a) + (b) + (c)] (2) Here, ( C1) represents the number of moles of the structural unit (c1) containing a bifunctional (meth) acrylate group in the side chain. The curable resin composition of the first aspect of the invention, wherein the amount of the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group in the component (A) is as shown in the following formula (3) The molar fraction M _b represents a soluble polyfunctional (meth) acrylate copolymer of 0.05 to 0.60; M _b = (b) / [(a) + (b) + (c)] (3). The curable resin composition of the first aspect of the invention, wherein the amount of the monofunctional (meth) acrylate (a) having an alicyclic structure in the component (A) is introduced by the following formula (4) The molar fraction M _a shown is a soluble polyfunctional (meth) acrylate copolymer of 0.05 to 0.60; M _a = (a) / [(a) + (b) + (c)] (4) . The sclerosing resin composition of claim 1, wherein the monofunctional (meth) acrylate (a) having an alicyclic structure is selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, and methyl group. Cyclohexyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, bicyclo methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure in a group of pentenyloxyethyl ester and dicyclopentanyl methacrylate. The sclerosing resin composition of claim 1, wherein the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is selected from the group consisting of 2-hydroxypropyl methacrylate and 2-hydroxy methacrylate. A monofunctional (meth) acrylate in a group of ethyl esters. The sclerosing resin composition of claim 1, wherein the aforementioned bifunctional (meth) acrylate (c) is selected from the group consisting of 1,4-butanediol diacrylate and 1,6-hexanediol diacrylic acid. Ester, 1,9-nonanediol diacrylic acid One or more bifunctional (meth) acrylates in the group of esters and dimethylol tricyclodecane diacrylate. The curable resin composition of the first aspect of the invention, wherein the monomer having one or more functional groups having a polymerizable unsaturated double bond as the component (B) is a monofunctional having an alicyclic structure. One or more (meth) acrylates selected from (meth) acrylate and bifunctional (meth) acrylate. The curable resin composition of claim 1 further contains a photopolymerization initiator as the component (C). A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 13. An optical material characterized by being formed from a cured product as in claim 14 of the patent application. An optical material according to claim 15 wherein the optical material is an optical plastic lens or enamel.