TWI618724B - Polyurethane compound, photosensitive resin composition, method for producing photosensitive resin composition, and cured product - Google Patents

Abstract

The present invention provides a polyurethane compound, a photosensitive resin composition containing the compound, a method for producing the photosensitive resin composition, and a hardened product of the composition. The polyurethane compound can be made with excellent flexibility, high weather resistance, and high light resistance. It can maintain transparency and is especially suitable for resin composition for optical applications. The polyurethane compound is a diol compound other than the hydrogenated polybutadiene polyol compound (A) and the polyisocyanate compound (B), the (meth) acrylate compound (C) having a hydroxyl group, and the compound (A) as an optional component. (D) Obtained by performing a reaction.

Description

Polyurethane compound, photosensitive resin composition, method for producing photosensitive resin composition, and cured product

The present invention relates to a method for producing a polyurethane compound, a photosensitive resin composition, and a photosensitive resin composition containing a urethane (meth) acrylate having a hydrogenated polybutadiene polyol as a main skeleton. And hardened. Furthermore, since the cured film of the resin composition of the present invention is excellent in terms of flexibility, transparency, moisture resistance, and adhesion to the substrate, and has less curing shrinkage, it is particularly useful as an optical film for a display device, etc. Useful for bonding applications.

Since the past, amine (meth) acrylates, which are reactants of polyol compounds, polyisocyanate compounds, and hydroxy (meth) acrylate-containing compounds, have been used in many applications such as coating agents, adhesives, and photoresists. For example, in the field of patent document 1, especially in the field of deterioration due to yellowing, especially in optical applications, the design is based on a highly transparent polyol compound and an aliphatic or alicyclic polyisocyanate (methyl) Acrylate compounds.

Furthermore, hydrogenated polybutadiene may be selected as a polyol compound to improve yellow discoloration or weather resistance when exposed to severe conditions. In Patent Document 2, an amine (meth) acrylate is produced using a hydrogenated polybutadiene polyol. About hardened materials, weather resistance Although it has excellent properties, the hydrogenated polybutadiene skeleton has very high hydrophobicity, and is considered to have limited compatibility with monomers or additives that can be formulated as a composition. In addition, the hydrogenated polybutadiene polyol used has a relatively high iodine value, and it is suggested that properties that satisfy the currently required weather resistance or light resistance may not be provided. Furthermore, since the resin of amine (meth) acrylate is manufactured without dilution, there is a possibility that the viscosity is high during actual industrialization, and problems may arise in terms of workability.

In recent years, research or practical use of amine (meth) acrylates for LCD (liquid crystal display) applications is being actively carried out. For example, in Patent Document 3, it is used for bonding an optical display or a touch sensor using a polybutadiene-based (meth) acrylate oligomer and a (meth) acrylate oligomer. A photocurable adhesive composition is used. Regarding amine (meth) acrylates, it is estimated that in the future, those having excellent flexibility and higher weather resistance or light resistance will also be required. Further, Patent Document 4 describes application of an amine (meth) acrylate using a polyhydric alcohol compound having no aromatic ring to an LCD optical member.

Patent Document 1: Japanese Patent No. 2582575

Patent Document 2: Japanese Patent No. 4868654

Patent Document 3: Japanese Patent Application Publication No. 2012-46658

Patent Document 4: Japanese Patent Application Laid-Open No. 2011-190421

As the optical component applications represented by these display applications, the (meth) acrylic acid amines are required to have higher weather resistance or light resistance, and to improve the physical properties of the cured film, and to improve the phase with other resins or monomers and additives. Solubility, and then imagine the actual production line during industrialization, and In the future, it is also required to design amine (meth) acrylate materials and compositions having excellent workability in detail.

An object of the present invention is to improve the above requirements, and to provide a polyurethane compound, a photosensitive resin composition containing the same, a method for manufacturing the photosensitive resin composition, and a cured product of the resin composition. The polyurethane compound can provide weather resistance or light resistance A cured film having excellent properties and excellent flexibility, and a resin composition having a low shrinkage upon curing.

The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, found that a resin composition having a specific compound and composition can solve the above-mentioned problems, thereby achieving the present invention.

That is, the present invention relates to the following:

(1) A polyurethane compound (E) obtained by reacting a compound (A) shown below with a compound (B), a compound (C), and a compound (D),

Compound (A): hydrogenated polybutadiene polyol compound

Compound (B): Polyisocyanate compound

Compound (C): (meth) acrylate compound having at least one hydroxyl group

Compound (D): a diol compound other than compound (A);

(2) The polyurethane compound (E) according to (1), wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less;

(3) The polyurethane compound (E) according to (1) or (2), wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound;

(4) The polyurethane compound (E) according to any one of (1) to (3), wherein the (meth) acrylate compound (C) having at least one hydroxyl group is 2-hydroxy (meth) acrylate Ethyl ester

(5) The polyurethane compound (E) according to any one of (1) to (4), wherein the compound (A) Other diol compounds (D) are polyether polyols;

(6) A photosensitive resin composition comprising a polyurethane compound (E) and a polymerizable compound (F) other than (E) according to any one of (1) to (5);

(7) The photosensitive resin composition according to (6), wherein the polymerizable compound (F) is an alkyl (meth) acrylate or an alkylene (meth) acrylate;

(8) A method for producing a photosensitive resin composition such as (6) or (7), characterized in that: a polyurethane compound (E) is synthesized in a polymerizable compound (F) mixed system;

(9) The photosensitive resin composition according to (6) or (7), which contains a photopolymerization initiator (G);

(10) A cured product, which is a cured product of the photosensitive resin composition according to any one of (6) to (8).

The cured film of the photosensitive resin composition containing the polyurethane compound of the present invention is excellent in softness, weather resistance and light resistance. In addition to optical applications that need to maintain transparency, it can also be used in inks, plastic coatings, paper printing, In various coating fields such as metal coating and furniture coating, linings, adhesives, etc., there are many fields such as insulating varnishes, insulating sheets, laminated boards, printed circuit boards, resist inks, and semiconductor sealants in the electronic equipment field.

The polyurethane compound (E) of the present invention is characterized in that hydrogenated polybutadiene The polyol (A) and the diol compound (D) other than the compound (A) are first reacted with the polyisocyanate compound (B) (hereinafter referred to as the first reaction), and then the remaining isocyanate groups are allowed to have at least one or more The hydroxyl (meth) acrylate compound (C) reacts with it (hereinafter referred to as a second reaction).

As the hydrogenated polybutadiene polyol (A) used in the first reaction of the present invention, it can be used as long as it is a hydrogenated reduction product of a general polybutadiene polyol. Especially for optical applications, it is preferably The number of residual double bonds is more preferably 20 or less, and even more preferably 15 or less. Regarding the molecular weight of (A), anyone who can obtain a molecular weight distribution can be used. Especially when the balance between flexibility and hardening is achieved, the number average molecular weight is preferably 500 to 5,000, particularly preferably 500. ~ 3000 people.

Specific examples of the diol compound (D) other than the compound (A) used in the first reaction of the present invention include polyethylene glycol, polybutylene glycol, polytetramethylene glycol, and polypropylene glycol. , Polyether polyols such as polyethylene glycol, Polyethylene glycol adipates, Poly 1,4-butanediol adipate, Polycaprolactone and other polyester polyols, Ethylene glycol, propylene glycol Diols such as butanediol, pentanediol, hexanediol and neopentyl glycol; cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, alcohol containing a spiro skeleton, tricyclodecane Aliphatic alcohols such as dimethyl alcohol and pentacyclopentadecane dimethanol, and alkylene oxide adducts thereof, hydrogenated polybutadiene diols, and the like, branched or linear long chain alkyl diols, bis Bisphenols such as phenol A and bisphenol F, and alkylene oxide adducts of bisphenols, polyhydric alcohols such as trimethylolpropane, bis (trimethylolpropane), neopentaerythritol, and dinepentaerythritol, And alkylene oxide adducts of these polyols, and polyester polyols obtained by reacting these polyols with polyacids such as adipic acid. Although not particularly limited, the cured product of the photosensitive resin composition of the present invention is preferably a polyether polyol in order to improve flexibility and compatibility.

Regarding the molecular weight of the diol compound (D) other than the compound (A), generally available molecular weight distribution can be used, especially when the balance between flexibility and hardening is achieved, the number average molecular weight is preferably 500 ~ 6000, especially 500 ~ 4000.

In addition, the diol compound (D) other than the compound (A) is particularly preferably a polyether polyol having a molecular weight of 500 to 4,000.

Here, in the present invention, when hydrogenated polybutadiene polyols (A) and diol compounds (D) other than (A) are used in the reaction, hydrogenated polybutadiene (A) and (A) other than The use ratio of the diol compound (D) is not particularly limited. The component (A): (D) is preferably 9.999: 0.001 to 2: 8 in terms of mole ratio, more preferably 9.999: 0.001 to 5: 5, especially It is preferably 9.999: 0.001 to 7: 3.

The polyisocyanate compound (B) used in the first reaction of the present invention is a compound containing two or more isocyanate groups in one molecule, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, These terpolymers, etc. The aliphatic diisocyanate compound herein means a diisocyanate compound in which an isocyanate group is bonded to a chain carbon atom, and a diisocyanate compound in which an isocyanate group is bonded to a carbon atom of a cyclic saturated hydrocarbon. The aromatic diisocyanate compound means an isocyanate compound in which an isocyanate group is bonded to a carbon atom of an aromatic ring.

Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene Diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecylmethylene diisocyanate, 2,2,4-trimethylcyclohexane diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4-trimethyl ether Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, etc.

Examples of the aromatic diisocyanate compound include toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, and 1, Diisocyanate monomers such as 6-benzene diisocyanate, 1,4-benzene diisocyanate, and 1,6-benzene diisocyanate.

Among them, the aliphatic diisocyanate compound and the terpolymer of the aliphatic diisocyanate compound are preferred because they make the weather resistance of the coating film good. Examples of the terpolymer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanate and the like. Specifically, hexamethylene diisocyanate or isophorone diisocyanate may be mentioned. Wait. These can be used individually or in the form of a mixture.

In the present invention, the first reaction is added in an equivalent relationship (B / (A + D)> 1: [NCO] / [OH] mole ratio) in which isocyanate groups remain after the reaction. If the addition ratio is increased, a large amount of unreacted polyisocyanate compound (B) may exist, which may affect the softness of the photosensitive resin composition. In addition, when the addition ratio is reduced, the molecular weight may increase, which may affect the curability of the photosensitive resin composition. Specifically, it is preferable that the OH group of the alcohol compound (A + D) is 0.1 to 0.9 mol with respect to 1.0 mol of the NCO group of the polyisocyanate compound (B).

In the present invention, the first reaction can be performed without a solvent. In order to increase the viscosity of the product and improve workability, it is preferred to use a polymerizable compound (F) in a solvent having no alcoholic hydroxyl group or described below. In progress. Specific examples of the solvent include acetone, methyl ethyl ketone, and methyl ethyl ketone. Ketones such as isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, Glycol ethers such as propylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; ethyl acetate, butyl acetate, methyl lysin acetate, ethyl lysin acetate, Butylcellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dialkyl glutarate, dioxane succinate Single or mixed organic solvents such as petroleum esters, dialkyl esters such as adipic acid esters, cyclic esters such as γ-butyrolactone, petroleum ether, petroleum brain, hydrogenated petroleum brain, solvents petroleum petroleum, etc. get on.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction was confirmed by a decrease in the amount of isocyanate. In addition, a catalyst may be added to shorten the reaction time. As this catalyst, either an alkaline catalyst or an acid catalyst can be used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, and chlorine. Lewis acid catalysts such as aluminum, tin octylate, octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. The addition amount of these catalysts is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight part of the diol compound (A + D) and the polyisocyanate compound (B).

The polyurethane compound (E) of the present invention can be obtained by reacting (second reaction) the (meth) acrylate compound (C) having at least one hydroxyl group with the remaining isocyanate group after the first reaction. .

The so-called used in the second reaction of the present invention has at least one hydroxyl group The (meth) acrylate compound (C) is a compound having at least one each of a hydroxyl group and a (meth) acrylate group in one molecule, and specific examples include 2-hydroxyethyl (meth) acrylate , Propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (methyl) Base) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, poly Ethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxyl Mono (meth) acrylate of glycols such as pivalic acid neopentyl glycol mono (meth) acrylate; trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (Meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate, glycerol mono (meth) Acrylic Ester, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, isopropyl Mono (meth) acrylates and di (meth) acrylates of triols such as tris (2-hydroxyethyl) cyanurate di (meth) acrylate, glycerol di (meth) acrylate, or Mono- and di (meth) acrylates in which some of the hydroxyl groups of these alcohols have been modified by alkyl or ε-caprolactone; neopentaerythritol mono (meth) acrylate, dinepentaerythritol mono (methyl) ) Acrylate, bis (trimethylolpropane) mono (meth) acrylate, neopentaerythritol di (meth) acrylate, dinepentaerythritol di (meth) acrylate, bis (trimethylol) Propane) di (meth) acrylate, neopentaerythritol tri (meth) acrylate, dinepentaerythritol tri (meth) acrylate, bis (trimethylolpropane) tri (meth) acrylate Esters, Dinepentaerythritol Tetrakis (methyl) propene The acrylates, bis (trimethylolpropane) tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bis (trimethylolpropane) hexa (meth) acrylate, etc. are Polyfunctional (meth) acrylic acid esters of quaternary or higher alcohols having hydroxyl groups, or hydroxyl-containing polyfunctional (meth) acrylic acid modified by alkyl or ε-caprolactone Esters, etc.

Among the aforementioned (meth) acrylate compounds (C) having at least one hydroxyl group, in terms of excellent curability and flexibility, 2-hydroxyethyl (meth) acrylate is particularly preferred. In terms of ease of work, the polymerizable compound (F) described below in the present invention may be added during the reaction.

The second reaction of the present invention is based on the equivalent relationship of the disappearance of the isocyanate group of the intermediate obtained after the first reaction. Specifically, it is preferable that the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group be 1.0 to 3.0 with respect to 1.0 mol of the NCO group of the intermediate obtained after the first reaction. The mol is more preferably 1.0 to 2.0 mol.

The second reaction of the present invention can also be performed in the absence of a solvent. In order to increase the viscosity of the product and improve workability, it is preferably performed in the above-mentioned solvent and / or in the polymerizable compound (F) described later in the present invention. . The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction was confirmed by a decrease in the amount of isocyanate. The catalyst may be added to shorten the reaction time.

To the acrylate compound used as a raw material, a polymerization inhibitor such as 4-methoxyphenol is usually added, and a polymerization inhibitor may also be added during the reaction. Examples of such a polymerization inhibitor include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-ditert-butyl- 4-cresol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenanthrene Wait. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.

The photosensitive resin composition of this invention may contain the polymerizable compound (F) other than the polyurethane compound (E) and (E) component of this invention as an arbitrary component. Specific examples of the polymerizable compound (F) that can be used include a compound having a (meth) acrylic acid group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester. Wait.

Specific examples of the compound having a (meth) acryloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (F-1); (methyl) ) Amine acrylate (F-2); epoxy (meth) acrylate (F-3); (poly) ether (meth) acrylate (F-4); alkyl (meth) acrylate or ( Alkyl methacrylate (F-5); (meth) acrylate (F-6) with aromatic ring; (meth) acrylate (F-7) with alicyclic structure, etc., but not Limited to these.

The reactants can be obtained under known reaction conditions.

The so-called (poly) ester (meth) acrylate (F-1) which can be used in combination with the photosensitive resin composition of the present invention is a general term for (meth) acrylates having one or more ester bonds in the main chain. The so-called (meth) acrylate (F-2) is a generic name for (meth) acrylates having one or more amine ester bonds in the main chain, and the so-called epoxy (meth) acrylate (F-3) It is used as a general name for (meth) acrylates obtained by reacting an epoxy compound having more than one function with (meth) acrylic acid. The so-called (poly) ether (meth) acrylate (F-4) is used as General term for (meth) acrylates with more than one ether bond in the main chain. The so-called (meth) acrylic acid alkyl esters or (meth) acrylic acid alkyl diesters (F-5) are linear as the main chain. Alkyl, branched alkyl, linear or (meth) acrylic acid esters which may have a halogen atom and / or a hydroxyl group at the terminal. The so-called (meth) acrylic acid esters (F-6) with aromatic rings are used as A general term for (meth) acrylates having an aromatic ring in the main or branch chain, so-called (meth) acrylates (F) having an alicyclic structure (F -7) is a general term for (meth) acrylic acid esters that are used in the main chain or branched chain and have an alicyclic structure that can contain oxygen or nitrogen atoms in the constituent units.

Examples of the (poly) ester (meth) acrylate (F-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone modified 2-hydroxyethyl (meth) acrylate, cyclic Ethylene oxide and / or propylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified (meth) acrylate tetrahydrofuran methyl ester Monofunctional (poly) ester (meth) acrylates; hydroxyvalerate neopentyl glycol di (meth) acrylate, caprolactone modified hydroxyvalerate neopentyl glycol di ( (Meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate; ε-caprolactone, γ-butyrate of 1 mol or more to trimethylolpropane or glycerol Mono-, di-, or tri (meth) acrylates of triols obtained from cyclic lactone compounds such as lactones and δ-valerolactones; 1 mole of neopentyltetraol or bis (trimethylolpropane) Mono-, di-, tri-, or tetra- (meth) acrylates of tetraols obtained by forming cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or more; Addition of 1 neomole of dipentaerythritol to 1 mole Mono- or poly (meth) acrylates of hexaols obtained from cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone; as (poly) ethylene glycol, (poly) Diol components such as propylene glycol, (poly) tetramethylene glycol, (poly) butanediol, 3-methyl-1,5-pentanediol, and hexanediol, and maleic acid, fumaric acid Acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, isophthalic acid- (Meth) acrylic esters of polyester polyols which are reactants of polybasic acids such as sodium sulfonic acid and these anhydrides; the above-mentioned diol component, polybasic acids and their anhydrides, and ε-caprolactone , Γ-butyrolactone, δ-valerolactone Polyfunctional (poly) esters (meth) acrylates such as (meth) acrylates of cyclic lactone-modified polyester diols composed of etc. are not limited thereto.

The (meth) acrylic acid amine ester (F-2) which can be used in combination with the photosensitive resin composition of the present invention is an hydroxy compound (F-2-a) and an isocyanate having at least one (meth) acryloxy group. General term for (meth) acrylates obtained by the reaction of compound (F-2-b).

Specific examples of the hydroxy compound (F-2-a) having at least one (meth) acryloxy group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Ester, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Various (meth) acrylate compounds having a hydroxyl group, such as propylene glycol mono (meth) acrylate, neopentaerythritol tri (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and A ring-opening reaction product of the (meth) acrylate compound having a hydroxyl group and ε-caprolactone, and the like.

Specific examples of the isocyanate compound (F-2-b) include, for example, p-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, and 2, Aromatic diisocyanates such as 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-bicyclo Diisocyanates of aliphatic or alicyclic structure such as hexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, and lysine diisocyanate; one or more biuret bodies of isocyanate monomer or A polyisocyanate such as an isocyanate body obtained by trimerizing the diisocyanate compound; a polyisocyanate or the like obtained by an amine esterification reaction of the isocyanate compound and the polyol compound.

In addition, when obtaining an amine (meth) acrylate, it is also optional in the reaction of the hydroxy compound (F-2-a) having a (meth) acryloxy group and the isocyanate compound (F-2-b). And react with the polyol.

Examples of usable polyols include neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol. 1 to 10 carbon alkanediols, triols such as trimethylolpropane, neopentyl tetraol, tricyclodecanedimethanol, bis [hydroxymethyl] cyclohexane and other alcohols having a cyclic skeleton; And with these polyols and acids (e.g. succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) Polyester polyol obtained by reaction, caprolactone alcohol obtained by reaction of polyol with ε-caprolactone, polycarbonate polyol (e.g., by 1,6-hexanediol and diphenyl carbonate Polycarbonate diols obtained by the reaction of esters) or polyether polyols (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.) and the like.

The epoxy (meth) acrylate (F-3) which can be used in combination with the photosensitive resin composition of the present invention is obtained by reacting an epoxy resin containing more than one functional epoxy group with (meth) acrylic acid. A general term for (meth) acrylates. Specific examples of the epoxy resin used as a raw material of the epoxy (meth) acrylate include hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and the like. Phenyl diglycidyl ether; bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-S epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane epoxy compounds and other bisphenol-type epoxy compounds; hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type Hydrogenated bisphenol type epoxy compounds such as epoxy resins, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compounds; brominated bisphenols -A type epoxy resin, brominated bisphenol-F type epoxy resin and other halogens Bisphenol-type epoxy compounds; alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compounds; 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether Ethers, diethylene glycol diglycidyl ether and other aliphatic diglycidyl ether compounds; polysulfide diglycidyl ether and other polysulfide diglycidyl ether compounds; phenol novolac epoxy resin, cresol novolac epoxy Resin, trihydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol-A novolac type epoxy resin, epoxy resin containing naphthalene skeleton, miscellaneous Ring epoxy resin and so on.

Examples of the (poly) ether (meth) acrylate (F-4) that can be used in combination with the photosensitive resin composition of the present invention include, for example, butoxyethyl (meth) acrylate and butoxytriethylene Alcohol (meth) acrylate, epichlorohydrin modified butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl Monofunctional (poly) ether (meth) acrylates such as carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate ; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, etc. Alkanediol di (meth) acrylates; from copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, polyisoprenediol, hydrogenated polyisoprenediol, polybutadiene diene Polyols such as alcohols, hydrogenated polybutadiene glycols and other hydrocarbon polyols and (meth) acrylic acid-derived polyfunctional (meth) acrylates; 1 mole of neopentyl glycol plus 1 mole Of the above Di (meth) acrylates of diols made from cyclic ethers such as ethylene oxide, propylene oxide, and butylene oxide; bisphenol A, bisphenol F, bisphenol S, and other alkylene oxide modifications Plastidic (meth) acrylate; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S and other hydrogenated bisphenol epoxy Modified di (meth) acrylate; obtained by adding 1 mol or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide to trimethylolpropane or glycerol Mono-, di-, or tri- (meth) acrylates of triols; ethylene oxide, propylene oxide, cyclic epoxide added to 1 mol or more of neopentyl tetraol or bis (trimethylolpropane) Mono-, di-, tri-, or tetra- (meth) acrylates of triols formed from cyclic ether compounds such as oxetane; ethylene oxide, cyclic Polyfunctional (poly) ether (meth) acrylates such as 3 to 6-functional (meth) acrylates of hexaol, which are cyclic ether compounds such as oxypropane and butylene oxide.

Examples of the (meth) acrylic acid alkyl ester or (meth) acrylic acid alkyl diester (F-5) that can be used in combination with the photosensitive resin composition of the present invention include, for example, (meth) acrylic acid methyl ester and (formic acid) Base) ethyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Dodecyl ester, stearyl (meth) acrylate, isostearyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, (methyl) ) Monofunctional (meth) acrylates such as 1-adamantyl acrylate, 2-ethylhexylcarbitol (meth) acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (methyl) ) Acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octyl Glycol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate hydrocarbon diol di (meth) acrylates; trimethylolpropane mono (meth) acrylate ) Acrylate, di (meth) acrylate or tri (meth) acrylate (hereinafter, "multi" is used as a general term for di-, tri-, tetra- and other polyfunctional), glycerol mono (meth) acrylate or poly Mono (meth) acrylate, mono- or poly (meth) acrylate of neopentaerythritol, mono- or poly (meth) acrylate of bis (trimethylolpropane), mono- or poly (meth) acrylate of dipentaerythritol Mono- or poly (meth) acrylates of triols, tetraols, and hexaols, such as (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Hydroxyl-containing (meth) acrylic acids, such as esters and 4-hydroxybutyl (meth) acrylate.

Examples of the (meth) acrylic acid ester (F-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include, for example, monophenyl (meth) acrylate and benzyl (meth) acrylate Functional (meth) acrylates; di (meth) acrylates such as bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, and the like, but are not limited thereto.

Examples of the (meth) acrylate (F-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate. Monofunctional (meth) acrylates with alicyclic structure, such as esters, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate; hydrogenated bisphenol A, hydrogenated bisphenol F, etc. Bis (meth) acrylates of phenols; polyfunctional (meth) acrylates having a cyclic structure such as tricyclodecane dimethanol di (meth) acrylate; tetrahydrofuran methyl (meth) acrylate, etc. The alicyclic (meth) acrylate etc. which have an oxygen atom etc. in a structure are not limited to these.

In addition, as the compound having a (meth) acrylfluorenyl group that can be used in combination with the photosensitive resin composition of the present invention, in addition to the above compounds, for example, a (meth) acrylic polymer and a (meth) acrylic acid glycidyl can be used. Polyester (meth) acrylic polymer (meth) acrylic acid, such as reactant of ester or glycidyl (meth) acrylic acid polymer and (meth) acrylic acid; dimethylaminoethyl (meth) acrylate (Meth) acrylates with amine groups such as esters; iso (meth) acrylates such as tris (meth) acryloxyethyl isocyanurate; (meth) acrylic acid with polysiloxane skeleton Esters; polybutadiene (meth) acrylate, melamine (meth) acrylate, and the like.

Moreover, as a compound (F-8) containing a maleimide group which can be used together with the photosensitive resin composition of this invention, N-n-butyl maleimide and a N-hexyl group are mentioned, for example. Cis-butyleneimine, 2-cis-butyleneiminoethyl-ethyl carbonate, 2-cis-butyleneiminoethyl-propyl carbonate, N-ethyl- (2- Monofunctional aliphatic maleimides such as maleimide diethylimine ethyl) carbamate; alicyclic monofunctional maleimides such as N-cyclohexyl maleimide diimide Fluorenimines; N, N-hexamethylenebiscis-butenedifluorenimide, polypropylene glycol-bis (3-cis-butenediiminopropyl) ether, bis (2-cis-butene carbonate) Aliphatic dicis-butene difluorenimides such as diiminoethyl) esters; 1,4-dicis-butene difluoreniminocyclohexane, isophorone diamine bis (N-ethyl Cis-butene diimide) and other alicyclic bis-cis-butene diimide; maleic acid obtained by esterifying maleimide diacetimidic acid with polytetramethylene glycol Perylene imine compounds, by esterification of a tetraethylene oxide adduct of maleimide diiminohexanoic acid and neopentyl tetraol (Poly) ester (poly) maleimide compounds obtained by esterifying a carboxymaleimide diimide derivative with various (poly) alcohols, etc. , But not limited to these.

Examples of the (meth) acrylamido compound (F-9) that can be used in combination with the photosensitive resin composition of the present invention include acrylamide Monofunctional (meth) acrylamidoxines such as phthaloline and N-isopropyl (meth) acrylamidoxamine; polyfunctional (meth) acrylamidoxamines such as methylenebis (meth) acrylamidoxamine, etc. .

Examples of the unsaturated polyester (F-10) which can be used in combination with the photosensitive resin composition of the present invention include, for example, maleic acid such as dimethyl maleate and diethyl maleate Esters; esterification reactants of polyunsaturated carboxylic acids such as maleic acid, fumaric acid and polyhydric alcohols.

The polymerizable compound (F) which can be used in combination with the photosensitive resin composition of the present invention is preferably an alkyl (meth) acrylate or an alkyl (meth) acrylate having a low viscosity and excellent light resistance and workability. (F-5) is used in combination, but it is not limited to the above-mentioned compound, and if it is a compound having copolymerizability with the above-mentioned (E) component, the one or more compounds may be used in combination without particular limitation.

Among them, a compound having a long chain (meth) acryloxy group of C5 to C35, more preferably C15 to C35, such as alkyl (meth) acrylate or alkyl (meth) acrylate diester, is suitable. The reason is that by having such a structure, a photosensitive resin composition having excellent compatibility and transparency can be obtained.

Regarding the photosensitive resin composition of the present invention, the ratio of the components (E) and (F) is not particularly limited, and it is preferably contained in an amount of 10 to 2000% by weight based on 100% by weight of the (E) component. %, Particularly preferably 20 to 1000% by weight.

Specific examples of the photopolymerization initiator (G) used in the photosensitive resin composition of the present invention include benzoin such as benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether, and benzoin isobutyl ether; phenethyl Ketone, 2,2-diethoxy-2-phenylacetophenone, 1,1-cycloacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxybenzene Ethyl ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenones such as phosphonopropane-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone; 2,4- Diethyl-9-oxysulfur , 2-isopropyl-9-oxysulfur , 2-chloro-9-oxysulfur 9-oxysulfur Class; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenone, 4-benzylmethyl-4'-methyldiphenylsulfide Dibenzophenones such as bismethylaminobenzophenone; 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,4,6-trimethylbenzyl) -Phosphine oxides such as phenylphosphine oxide and the like. As these addition ratios, when the solid content of the photosensitive resin composition is 100% by weight, it is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight.

These can be used alone or in the form of a mixture of two or more, and can be used with tertiary amines such as triethanolamine, methyldiethanolamine, N, N-dimethylaminobenzoate, N, N-di Accelerators such as benzoic acid derivatives such as methylamylbenzoate and the like are used in combination. As an addition amount of these accelerators, if necessary, it is added in an amount of 100% by weight or less based on the photopolymerization initiator (G).

Further, as for the photosensitive resin composition of the present invention, non-reactive compounds, inorganic fillers, organic fillers, silane coupling agents, adhesion-imparting agents, antifoaming agents, leveling agents, plasticizers, Antioxidants, UV absorbers, flame retardants, pigments, dyes, etc.

Specific examples of the non-reactive compound include liquid or solid oligomers or resins having low reactivity or non-reactivity, and examples thereof include alkyl (meth) acrylate copolymers, epoxy resins, Liquid polybutadiene, dicyclopentadiene derivatives, saturated polyester oligomers, Xylene resin, polyurethane polymer, ketone resin, diallyl phthalate polymer (DAP resin), petroleum resin, rosin resin, fluorine oligomer, silicon oligomer, phthalate , Phosphate esters, glycol esters, citrates, aliphatic dibasic esters, fatty acid esters, epoxy plasticizers, castor oils, terpene-based hydrogenated resins, and polyisoprene Backbone, polybutadiene backbone or xylene backbone oligomer or polymer and its esterification, butadiene homopolymer, epoxy modified polybutadiene, butadiene-styrene random copolymer, Softening agents such as polybutene are not limited to these. The weight ratio of this component in an ultraviolet curable resin composition is 10-80 weight% normally, Preferably it is 10-70 weight%.

Examples of the inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, and aluminum oxide. , Glass, mica, barium sulfate, alumina white, zeolite, silica balloon, glass hollow ball, and the like. In these inorganic fillers, a method such as adding a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a zirconate-based coupling agent, etc., and reacting them may also include a halogen group and an epoxy group. , Hydroxyl, thiol functional groups.

Examples of the organic filler include benzoguanidine Resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene-acrylic copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluorine resin, nylon 12, nylon 6/66, phenol resin, epoxy resin, amine ester resin, polyimide resin, etc.

Examples of the silane coupling agent include silane coupling agents such as γ-glycidyloxypropyltrimethoxysilane and γ-chloropropyltrimethoxysilane, and tetrakis (2,2-diallyloxymethyl- 1-Butyl) bis (di-tridecyl) phosphite titanate (tetra (2,2-diallyloxymethylene-1-butyl) bis (ditridecyl) phosphite titanate) Titanate-based coupling agents such as bis (dioctyl pyrophosphate) ethylene titanate; aluminum-based coupling agents such as acetoalkoxydiisopropoxyaluminum; acetoacetone-zirconium Zirconium-based coupling agents such as complexes.

Regarding adhesion-imparting agents, defoamers, leveling agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, pigments, and dyes that can be used in the photosensitive resin composition of the present invention, as long as they are known and used, Any one can be used without particular limitation as long as the hardenability and resin characteristics are not impaired.

In order to obtain the photosensitive resin composition of the present invention, the above-mentioned respective components may be mixed, and the order or method of mixing is not particularly limited.

When various additives are present in the composition, the weight ratio of the various additives in the light-curing transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and more preferably 0.02 to 0.5% by weight. %.

The photosensitive resin composition of the present invention does not substantially require a solvent, but ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, and benzene and toluene can also be used. The photosensitive resin composition of the present invention is used by diluting the photosensitive resin composition of the present invention with aromatic hydrocarbons such as xylene, and other commonly used organic solvents.

The photosensitive resin composition of the present invention can be polymerized by irradiating ultraviolet or visible light having a wavelength of 180 to 500 nm. In addition, it may be hardened by irradiating energy rays other than ultraviolet rays or heat.

Examples of the light or ultraviolet light source with a wavelength of 180 to 500 nm include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, excimer lamps, and short-arc lamps. , Helium-cadmium laser, argon laser, quasi-point Sub-laser, sunlight.

The photosensitive resin composition of the present invention is excellent in flexibility, has high weather resistance and light resistance, and can be used for inks, plastic coatings, paper printing, metal coating, and furniture coatings in addition to optical applications that require maintaining transparency. In various fields such as coatings, linings, adhesives, and electronic equipment, insulating varnishes, insulating sheets, laminated boards, printed boards, resist inks, and semiconductor sealants, etc. As a more specific application, it is applicable to ink fields such as planographic ink, flexographic ink, gravure ink, screen ink, etc., light card field, paper coating agent field, woodworking coating field, beverage can coating agent or printing ink field. , Flexible packaging film coating agent, printing ink or adhesive, thermal paper, coating agent for thermal film, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel type Air gap fillers for display devices such as image display devices (fillers for gaps between display devices and surface plates) are useful.

Examples

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example 1

To a reactor equipped with a reflux cooler, a stirrer, a thermometer, and a temperature adjustment device, GI-2000 (iodine value: 12.2, hydroxyl value: 46.8 mg, manufactured by Japan Soda Co., Ltd., which is a hydrogenated polybutadiene polyol compound, was added. ‧KOH / g) 569.73g (0.24mol), as a diol compound, Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9mg‧KOH / g), 7.50g (0.0024mol) manufactured by Asahi Glass Co., Ltd., as a polymerizable compound 171.49 g of S-1800A (isostearyl acrylate) manufactured by Shin Shin Nakamura Chemical Co., Ltd. and 0.41 g of 4-methoxyphenol as a polymerization inhibitor were stirred until uniform, and the internal temperature was set to 50 ° C. Then, add as 80.03 g (0.36 mol) of isophorone diisocyanate of the polyisocyanate compound was reacted at 80 ° C. until the target NCO content was reached. Next, 28.70 g (0.247 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one hydroxyl group, and octanoic acid as an amine esterification reaction catalyst were added. 0.20 g of tin was reacted at 80 ° C, and when the NCO content was 0.1% or less, it was regarded as the end point of the reaction to obtain a polyurethane compound (E-1).

Synthesis Example 2

To a reactor equipped with a reflux cooler, a stirrer, a thermometer, and a temperature adjustment device, GI-2000 (iodine value: 12.2, hydroxyl value: 46.8 mg, manufactured by Japan Soda Co., Ltd., which is a hydrogenated polybutadiene polyol compound, was added. ‧KOH / g) 545.99g (0.23mol), Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9mg‧KOH / g), 7.19g (0.0023mol), manufactured by Asahi Glass Co., Ltd. as a diol compound, as a polymerizable compound 208.51 g of S-1800A (isostearyl acrylate) manufactured by Shin Shin Nakamura Chemical Co., Ltd. and 0.37 g of 4-methoxyphenol as a polymerization inhibitor were stirred until uniform, and the internal temperature was set to 50 ° C. Then, 61.35 g (0.28 mol) of isophorone diisocyanate as a polyisocyanate compound was added, and the reaction was performed at 80 ° C. until the target NCO content was reached. Next, 11.00 g (0.095 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one hydroxyl group, and octanoic acid as an amine esterification reaction catalyst were added. 0.20 g of tin was reacted at 80 ° C, and when the NCO content was 0.1% or less, it was regarded as the end point of the reaction to obtain a polyurethane compound (E-2).

Synthesis Example 3

In a reactor equipped with a reflux cooler, a stirrer, a thermometer, and a temperature adjustment device, add KASAOL HLBH-P 2000 (iodine value: 13.5, hydroxyl value: 0.89 meq / g) manufactured by CRAY VALLEY as a hydrogenated polybutadiene polyol compound was added with 511.69 g (0.23 mol) as a glycol compound. Asahi Glass Co., Ltd. Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg‧KOH / g) 7.19 g (0.0023 mol), S-1800A (isostearyl acrylate) manufactured by Shin Nakamura Chemical Co., Ltd. as a polymerizable compound, 197.08 g 0.36 g of 4-methoxyphenol as a polymerization inhibitor, stir until homogeneous, and set the internal temperature to 50 ° C. Then, 61.35 g (0.28 mol) of isophorone diisocyanate as a polyisocyanate compound was added, and the reaction was performed at 80 ° C. until the target NCO content was reached. Next, 11.00 g (0.095 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one hydroxyl group, and octanoic acid as an amine esterification reaction catalyst were added. 0.20 g of tin was reacted at 80 ° C, and when the NCO content was 0.1% or less, it was regarded as the end point of the reaction to obtain a polyurethane compound (E-3).

Deployment example 1

20 parts by mass of the polyurethane compound (E-1) of Synthesis Example 1, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin Nakamura Chemical Co., Ltd., and Blemmer LA (acrylic laurel) manufactured by Nippon Oil Co., Ltd. 10 parts by mass, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yasuhara Chemical Co., Ltd., LV-100 (polybutene) manufactured by JX Nippon Nissei Energy Co., Ltd. 10 parts by mass, 20 parts by mass of GI-2000 (1,2-hydrogenated polybutadiene glycol) manufactured by Japan Soda Co., Ltd., SPEEDCURE TPO (2,4,6-trimethylbenzidine) manufactured by LAMBSON 0.5 parts by mass of diphenylphosphine oxide), 0.5 parts by mass of IRGACURE 184 (1-hydroxycyclohexylphenyl ketone) manufactured by BASF Corporation, and PBD (2- (4-biphenyl)- 5-(4-Third-butylphenyl) -1,3,4- Diazole) 0.05 parts by mass was heated to 70 ° C. and mixed to obtain the resin composition of the present invention. The viscosity of this resin composition was 3200 mPa‧s.

Deployment example 2

20 parts by mass of the polyurethane compound (E-2) of Synthesis Example 2, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin Nakamura Chemical Co., Ltd., and Blemmer LA (acrylic laurel) manufactured by Nippon Oil Co., Ltd. 10 parts by mass, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yasuhara Chemical Co., Ltd., LV-100 (polybutene) manufactured by JX Nippon Nissei Energy Co., Ltd. 10 parts by mass, 20 parts by mass of GI-2000 (1,2-hydrogenated polybutadiene glycol) manufactured by Japan Soda Co., Ltd., SPEEDCURE TPO (2,4,6-trimethylbenzidine) manufactured by LAMBSON 0.5 parts by mass of diphenylphosphine oxide), 0.5 parts by mass of IRGACURE 184 (1-hydroxycyclohexylphenyl ketone) manufactured by BASF Corporation, and PBD (2- (4-biphenyl)- 5- (4-Third-butylphenyl) -1,3,4- Diazole) 0.05 parts by mass was heated to 70 ° C. and mixed to obtain the resin composition of the present invention. The viscosity of this resin composition was 5000 mPa‧S.

Deployment example 3

20 parts by mass of the polyurethane compound (E-3) of Synthesis Example 3, 22 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin Nakamura Chemical Co., Ltd., and Blemmer LA (acrylic laurel) manufactured by Nippon Oil Co., Ltd. 10 parts by mass, 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yasuhara Chemical Co., Ltd., LV-100 (polybutene) manufactured by JX Nippon Nissei Energy Co., Ltd. 10 parts by mass, 20 parts by mass of GI-2000 (1,2-hydrogenated polybutadiene glycol) manufactured by Japan Soda Co., Ltd., SPEEDCURE TPO (2,4,6-trimethylbenzidine) manufactured by LAMBSON 0.5 parts by mass of diphenylphosphine oxide), 0.5 parts by mass of IRGACURE 184 (1-hydroxycyclohexylphenyl ketone) manufactured by BASF Corporation, and PBD (2- (4-biphenyl)- 5- (4-Third-butylphenyl) -1,3,4- Diazole) 0.05 parts by mass was heated to 70 ° C. and mixed to obtain the resin composition of the present invention. The viscosity of this resin composition was 5500 mPa‧s.

Preparation Examples 1 to 3 are shown in Table 1, and the following evaluations were performed.

(Viscosity) The measurement was performed at 25 ° C using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(Refractive index) The refractive index (25 ° C) of the resin was measured using an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(Hardening Shrinkage Ratio) Two pieces of 1 mm-thick glass slides coated with a fluorine-based release agent were prepared, and UV curing obtained by applying a film thickness of 200 μm on one of the release agent-coated surfaces was obtained. Type resin composition. After that, the two glass slides were bonded so that the release agent-coated surfaces faced each other. The resin composition was irradiated with ultraviolet light having a cumulative light amount of 3000 mJ / cm ² through a glass using a high-pressure mercury lamp (80 W / cm, no ozone) to harden the resin composition. Thereafter, the two glass slides were peeled off to produce a cured product for measuring the specific gravity of the film. The specific gravity (DS) of the cured product was measured in accordance with the JIS K7112 B method. The liquid specific gravity (DL) of the resin composition was measured at 25 ° C. From the measurement results of DS and DL, the cure shrinkage was calculated according to the following formula, and the result was less than 2.5%.

Hardening shrinkage (%) = (DS-DL) ÷ DS × 100

(Rigidity) Two pieces of the PET film subjected to the release treatment were prepared, and the obtained UV-curable resin composition was applied on the release surface of one of them so that the film thickness became 200 μm. Thereafter, the two PET films were bonded so that the respective release surfaces faced each other. The resin composition was irradiated with ultraviolet light with a cumulative light amount of 3000 mJ / cm ² through a PET film using a high-pressure mercury lamp (80 W / cm, no ozone) to harden the resin composition. After that, the two PET films were peeled to produce a cured product for measuring the rigidity. The rigidity was measured by ARES (manufactured by TA Instruments).

(Transmittance) Two glass slides having a thickness of 1 mm were prepared, and the obtained UV-curable resin composition was applied on one of the glass slides so that the film thickness after curing became 200 μm. Thereafter, the two slides were bonded together. A high-pressure mercury lamp (80 W / cm, ozone-free) was irradiated through the glass with ultraviolet light having a cumulative light amount of 3000 mJ / cm ² to harden the resin composition, thereby producing a hardened material for measuring transmittance. About the transparency of the obtained hardened | cured material, the transmittance | permeability in the wavelength region of 400-800nm and 400-450nm was measured using the spectrophotometer (U-3310, Hitachi High-Technologies Co., Ltd.). As a result, the transmittance of 400 to 800 nm was 90% or more, and the transmittance of 400 to 450 nm was 90% or more.

(Heat resistance, moisture resistance adhesiveness) Prepare a glass slide with a thickness of 1mm and a glass plate with a thickness of 1mm, or a glass plate with a thickness of 1mm with a polarizing film on one side, and apply a film thickness of 200 μm on one of them After the ultraviolet curable resin composition obtained by the cloth, the other was bonded to the coated surface. The resin composition was irradiated with ultraviolet light having a cumulative light amount of 3000 mJ / cm ² through a glass through a high-pressure mercury lamp (80 W / cm, ozone-free) to harden the resin composition to prepare a sample for evaluation of adhesion. This was used for a heat resistance test at 85 ° C, a humidity resistance test at 60 ° C, and 90% RH, and left to stand for 100 hours. With respect to this evaluation sample, peeling of the cured resin from the glass or the polarizing film was visually confirmed, but no peeling was observed.

The present invention will be described in detail with reference to specific aspects, but it is clear to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

In addition, this application is based on Japanese Patent Application (2013-252028) filed on Dec. 5, 2013, and the entirety thereof is incorporated by reference. Also, all references cited herein are incorporated herein in their entirety.

[Industrial availability]

The photosensitive resin composition containing a polyurethane compound of the present invention is useful as an optical member because it has excellent flexibility, high weather resistance, light resistance, and excellent transparency. Furthermore, the hardened | cured material of the photosensitive resin composition of this invention is useful as an adhesive agent for bonding a transparent display substrate.

Claims (12)

A polyurethane compound (E) obtained by reacting the compound (A) and the compound (D) shown below with the compound (B), and then reacting the compound (C) with the remaining isocyanate group, Compound (A): hydrogenated polybutadiene polyol compound Compound (B): polyisocyanate compound Compound (C): (meth) acrylate compound having at least one or more hydroxyl groups Compound (D): polyether Polyols; and the OH group of the alcohol compound (A + D) is 0.1 to 0.9 mol with respect to 1.0 mol of the NCO group of the polyisocyanate compound (B). For example, the polyurethane compound (E) of item 1 of the patent application range, wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less. For example, the polyurethane compound (E) of the first patent application range, wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound. For example, the polyurethane compound (E) of item 2 of the patent application scope, wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound. The polyurethane compound (E) according to any one of claims 1 to 4, wherein the (meth) acrylate compound (C) having at least one hydroxyl group is 2-hydroxyethyl (meth) acrylate . For example, the polyurethane compound (E) in the first patent application range has a hydroxyl value of 35.9 mg‧KOH / g or less. For example, the polyurethane compound (E) of the first patent application range, wherein the compound (A): The compound (D) has a molar ratio of 9.999: 0.001 to 7: 3. A photosensitive resin composition containing a polyurethane compound (E) according to any one of claims 1 to 7 and a polymerizable compound (F) other than (E). For example, the photosensitive resin composition according to item 8 of the application, wherein the polymerizable compound (F) is an alkyl (meth) acrylate or an alkylene (meth) acrylate. For example, the photosensitive resin composition according to item 8 or 9 of the patent application scope, which contains a photopolymerization initiator (G). A method for producing a photosensitive resin composition with a scope of patent application No. 8 or 9, which is to synthesize a polyurethane compound (E) in a polymerizable compound (F) mixed system. A hardened product is a hardened product of a photosensitive resin composition according to any one of claims 8 to 10.