WO2016031952A1

WO2016031952A1 - Polyurethane compound and resin composition containing same

Info

Publication number: WO2016031952A1
Application number: PCT/JP2015/074357
Authority: WO
Inventors: 英照亀谷; 貴文水口; 隼本橋
Original assignee: 日本化薬株式会社
Priority date: 2014-08-29
Filing date: 2015-08-28
Publication date: 2016-03-03
Also published as: KR20170047240A; JP2016050251A; TW201615682A; CN107075069A; JP6271375B2

Abstract

This invention provides a polyurethane resin (E) that has excellent flexibility, weather resistance, and light resistance, can maintain transparency, and is suitable for use in optical applications. The polyurethane resin (E) is obtained by reacting a compound (A), a compound (B), and a compound (C), based on the relationship (number of moles of isocyanate groups of (B)) > (total number of moles of hydroxyl groups of (A) and (C)), and then reacting a compound (D). Compound (A): a polyol compound; compound (B): a polyisocyanate compound; compound (C): a (meth)acrylate compound that has at least one hydroxyl group; and compound (D): a polyol compound.

Description

Polyurethane compound and resin composition containing the same

This invention relates to the resin composition containing the urethane (meth) acrylate which introduce | transduced the polyol by specific component ratio. Furthermore, since the cured film of the resin composition of the present invention is excellent in flexibility, transparency, moisture resistance, adhesion to a substrate, and has little curing shrinkage, it is particularly useful for bonding applications such as optical films for display devices. is there.

Conventionally, urethane (meth) acrylate, which is a reaction product of a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound, has been widely used for applications such as coating agents, adhesives, and photoresists. For example, in the field where degradation due to yellowing such as Patent Document 1 is particularly problematic, a urethane (meth) acrylate compound is designed based on a highly transparent polyol compound and an aliphatic or alicyclic polyisocyanate. To do.

In some cases, hydrogenated polybutadiene is selected as a polyol compound to improve yellowing or weather resistance when exposed to more severe conditions. In Patent Document 2, urethane (meth) acrylate is produced using hydrogenated polybutadiene polyol. Although it is excellent in weather resistance as a cured product, it is considered that the hydrogenated polybutadiene skeleton has very high hydrophobicity and is limited in compatibility with monomers and additives that can be blended as a composition. In addition, since it is produced as a urethane (meth) acrylate resin without dilution, the actual industrialization has a high viscosity and may cause problems in terms of workability.

In recent years, studies and achievements of urethane (meth) acrylate in LCD (liquid crystal display) applications have become active. For example, in patent document 3, it is utilized as a photocurable adhesive composition used for bonding of an optical display or a touch sensor using a polybutadiene-based (meth) acrylate oligomer and a urethane (meth) acrylate oligomer. As urethane (meth) acrylate, it is presumed that a product having excellent flexibility and higher weather resistance and light resistance will be required in the future. Patent Document 4 describes the application of urethane (meth) acrylate using a polyol compound having no aromatic ring to an LCD optical member.

Japanese Patent No. 25582575 Japanese Patent No. 4868654 Japanese Unexamined Patent Publication No. 2012-46658 Japanese Unexamined Patent Publication No. 2011-190421

Optical member applications such as these display applications require urethane (meth) acrylates to have higher weather resistance, light resistance, improved cured film properties, and improved compatibility with other resins, monomers, and additives. Further, in the industrialization, detailed design of urethane (meth) acrylate materials and compositions having excellent workability will be required in the future, assuming an actual production line.

An object of the present invention is to provide a resin composition that improves the above requirements, provides a cured film having excellent weather resistance and light resistance and excellent flexibility, and has a low shrinkage upon curing.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

That is, the present invention provides (1) the following compound (A), compound (B), and compound (C): (number of moles of isocyanate group of compound (B))> (number of moles of hydroxyl group of compound (A)) + Polyurethane resin (E) obtained by reacting in the relationship of + number of moles of hydroxyl group of compound (C) and then reacting with compound (D),
Compound (A): Polyol compound compound (B): Polyisocyanate compound compound (C): (Meth) acrylate compound compound (D) having at least one hydroxyl group: Polyol compound (2) Polyol compound (A) is hydrogenated The polyurethane resin (E) according to (1), which contains at least one polyol compound selected from polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol,
(3) The polyurethane resin (E) according to (1) or (2), wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound,
(4) The polyurethane resin (E) according to any one of (1) to (3), wherein the (meth) acrylate compound (C) having at least one hydroxyl group is 2-hydroxyethyl (meth) acrylate,
(5) The polyurethane according to any one of (1) to (4), wherein the polyol compound (D) contains at least one polyol compound selected from hydrogenated polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol. Resin (E),
(6) Polyol compound with respect to the number of moles of isocyanate group remaining by (number of moles of isocyanate group of compound (B)) − (number of moles of hydroxyl group of compound (A) + number of moles of hydroxyl group of compound (C)) The polyol compound (D) is charged so that the number of moles of hydroxyl groups in (D) exceeds the number of remaining isocyanate groups, and the isocyanate group and unreacted polyol compound (D) are contained as a plasticizer (1). To a resin composition (F) containing the polyurethane resin (E) according to any one of (5),
(7) A photosensitive resin containing the polyurethane resin (E) according to any one of (1) to (5) or the resin composition (F) according to (6) and a polymerizable compound (G) other than (E). Functional resin composition,
(8) The photosensitive resin composition according to (7), wherein the polymerizable compound (G) is an alkyl (meth) acrylate or an alkylene (meth) acrylate,
(9) The photosensitive resin composition according to (7) or (8), which contains a photopolymerization initiator (H),
(10) A cured product of the photosensitive resin composition according to any one of (7) to (9),
About.

The cured film of the photosensitive resin composition containing the polyurethane compound of the present invention is excellent in flexibility, weather resistance and light resistance, and in addition to optical applications that need to maintain transparency, ink, plastic paint, paper printing , Metal coating, furniture coating, various coating fields, linings, adhesives, as well as many fields such as insulating varnishes, insulating sheets, laminates, printed circuit boards, resist inks, and semiconductor encapsulants in the electronics field Is possible.

The polyurethane resin (E) of the present invention first reacts with the polyol compound (A) and the polyisocyanate compound (B) (hereinafter referred to as the first reaction), and then has at least one hydroxyl group for the remaining isocyanate groups. The (meth) acrylate compound (C) having a reaction (hereinafter referred to as a second reaction), and the polyol compound (D) is reacted with a remaining isocyanate group (hereinafter referred to as a third reaction). And

Examples of the polyol compound (A) used in the first reaction of the present invention include polyether polyols such as polybutylene glycol, polytetramethylene glycol, polypropylene glycol and polyethylene glycol, polyethylene glycol adipate, poly 1,4- Polyester polyols such as butanediol adipate and polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentylglycol, cyclohexanedimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton -Containing alcohols, alicyclic alcohols such as tricyclodecane dimethylol and pentacyclopentadecane dimethylol and their alkylene oxy Iodide adduct, branched or linear long chain alkyl polyol such as polybutadiene polyol and hydrogenated polybutadiene polyol, bisphenol such as bisphenol A and bisphenol F, and alkylene oxide adduct of bisphenol, trimethylolpropane, ditrimethylolpropane, penta Examples thereof include polyols such as erythritol and dipentaerythritol, alkylene oxide adducts of these polyols, polyester polyols obtained by reaction of these polyols with polybasic acids such as adipic acid, and polycarbonate polyols. Although not particularly limited, hydrogenated polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol are preferable in maintaining the flexibility and transparency of the photosensitive resin composition of the present invention, and hydrogen is used from the viewpoint of imparting flexibility. Polybutadiene polyol and polybutadiene polyol are particularly preferred, and polycarbonate polyol is particularly preferred from the viewpoint of imparting heat resistance, hardness and adhesive strength.
When hydrogenated polybutadiene polyol is used, the hydroxyl value is preferably 10 to 300 mg · KOH / g, more preferably 15 to 250 mg · KOH / g, and particularly preferably 20 to 150 mg · KOH / g.
When polycarbonate polyol is used, the hydroxyl value is preferably 20 to 150 mg · KOH / g.

The polyol compound (A) can be used singly or in combination as long as it is the above compound. Regarding the molecular weight of (A), all generally available molecular weight distributions can be used. When the balance of properties is balanced, the number average molecular weight is preferably from 300 to 6000, particularly preferably from 500 to 5000.

The polyisocyanate compound (B) used in the first reaction of the present invention is a compound comprising two or more isocyanate groups in one molecule, and examples thereof include aliphatic diisocyanate compounds and aromatic diisocyanates. Compounds, trimers thereof, and the like. The aliphatic diisocyanate compound as used 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, and an aromatic diisocyanate compound. Means an isocyanate compound in which an isocyanate group is bonded to a carbon atom of an aromatic ring. From the viewpoint of imparting transparency, an aliphatic diisocyanate compound is preferred.

Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene 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-dodecamethylene diisocyanate, 2,2,4-trimethylcyclohexane Diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diiso Aneto, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate and the like. Of these, isophorone diisocyanate is preferred.

Examples of the aromatic diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene. And diisocyanate monomers such as diisocyanate.

Among these, an aliphatic diisocyanate compound and a trimer of the aliphatic diisocyanate compound are preferable because the weather resistance of the coating film is improved. Examples of the trimer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanates, and specific examples include hexamethylene diisocyanate and isophorone diisocyanate. These may be used alone or in a mixture.

In the present invention, the first reaction is carried out in an equivalent relationship (B / A> 1: [NCO] / [OH] molar ratio) such that an isocyanate group remains after the reaction. When the charging ratio is increased, a large amount of unreacted polyisocyanate compound (B) is present, which may affect the flexibility of the photosensitive resin composition. Further, when the preparation ratio is reduced, the molecular weight is increased, which may affect workability deterioration and curability associated with an increase in the viscosity of the photosensitive resin composition. Specifically, the OH group of the polyol compound (A) is preferably 0.1 to 0.9 mol, preferably 0.4 to 0.00 mol per 1.0 mol of the NCO group of the polyisocyanate compound (B). More preferably, it is 7 mol.

In the present invention, the first reaction can be carried out in the absence of a solvent. However, in order to improve the workability and the viscosity of the product is high, the following compound in a solvent having no alcoholic hydroxyl group or a polymerizable compound (described later) G) can also be performed. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol. Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, esters such as dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Can be carried out alone or in a mixed organic solvent.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is 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 acidic catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, octyltin trilaurate, dibutyltin dilaurate, Mention may be made of Lewis acid catalysts such as octyltin diacetate. The amount of these catalysts added is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the polyol compound (A) and the polyisocyanate compound (B).

The (meth) acrylate compound (C) having at least one hydroxyl group used in the second reaction of the present invention is a compound having at least one hydroxyl group and one (meth) acrylate in each molecule. Specifically, 2-hydroxyethyl (meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono ( (Meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene 2 such as polyglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate hydroxypivalate Mono (meth) acrylates of monohydric alcohols;

Trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate, glycerin mono (meta) ) Acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, glycerin Mono- and di (meth) acrylates of trivalent alcohols such as di (meth) acrylate, and some of the hydroxyl groups of these alcohols are alkyl groups or ε-caprolactates In modified mono- and di (meth) acrylate;

Pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa Polyfunctional alcohols such as (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc. Data) and those having a hydroxyl group in acrylates, polyfunctional (meth) acrylate having a hydroxyl group partially modified with an alkyl group and ε- caprolactone hydroxyl groups of these alcohols, and the like.

Of the above (meth) acrylate compound (C) having at least one hydroxyl group, one hydroxyl group is preferred, and 2-hydroxyethyl (meth) acrylate is particularly preferred from the viewpoint of excellent curability and flexibility. . From the viewpoint of easy workability, a polymerizable compound (G) described later in the present invention may be added during the reaction.

The second reaction of the present invention is carried out in an equivalent relationship in which less than an equivalent amount of hydroxyl groups react with the isocyanate group of the intermediate obtained after the first reaction. Specifically, preferably, the OH group of the (meth) acrylate compound (C) having at least one hydroxyl group is 0.01 to 0.00 with respect to 1.0 mol of the NCO group of the intermediate obtained after the first reaction. It is 99 mol, more preferably 0.1 to 0.9 mol, and particularly preferably 0.4 to 0.6 mol.

The second reaction of the present invention can also be carried out in the absence of a solvent, but the product has a high viscosity and the above-described solvent and / or polymerizable compound (G) described later in the present invention for improving workability. It is preferable to carry out under mixing. The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. The aforementioned catalyst may be added for the purpose of shortening the reaction time.

Usually, a polymerization inhibitor such as 4-methoxyphenol has already been added to the (meth) acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, Examples include p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, and phenothiazine. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.

The polyurethane resin (E) of the present invention can be obtained by reacting the intermediate obtained in the second reaction with the polyol compound (D) (third reaction). As the polyol compound (D), one or more kinds of the same or different kinds as the above-described polyol compound (A) can be selected and used.
Here, the same thing as a polyol compound (A) can be used, The example is as above-mentioned. Here, the polyol compound (A) and the polyol compound (D) are the same type of compound (for example, polybutadiene polyol and polybutadiene polyol, polyether polyol and polyether polyol, polycarbonate polyol and polycarbonate polyol, etc.) or the same compound. Is preferred.

The third reaction of the present invention is charged in an equivalent relationship such that the isocyanate group of the intermediate obtained after the second reaction is eliminated. Specifically, the OH group of the polyol compound (D) is preferably 1.0 to 10.0 mol, more preferably 1.0 to 1.0 mol with respect to 1.0 mol of the NCO group of the intermediate obtained after the second reaction. The amount is 9.0 mol, particularly preferably 3.0 to 5.0 mol. At this time, since the excess polyol compound (D) that does not participate in the reaction remains in the system as a plasticizer, it is possible to obtain a resin composition (F) excellent in workability that is reduced in viscosity by adjusting the amount of preparation at a time. .

As the compound obtained by the first to third reactions of the present invention, the polyol compound (A) reacts with a part of the isocyanate groups of the polyisocyanate compound (B), and the remaining isocyanate groups have a hydroxyl group (meth). Since the polyurethane compound (U1) obtained by the reaction of the acrylate compound (C) and the polyol compound (A) reacts with the polyisocyanate in the first reaction, the isocyanate group of the polyisocyanate compound (B) is converted into the polyol compound (A). ) And a part of the terminal polyisocyanate compound (B) reacts with the (meth) acrylate compound (C) having a hydroxyl group to add a (meth) acryloyl group, and a polyol compound ( And a polyurethane compound (U2) obtained by reacting D).
In this case, the polyisocyanate compound (B) is preferably bifunctional. In this case, the resulting polyurethane compound having a (meth) acryloyl group contains a large amount of monofunctionality.
The obtained polyurethane compounds (U1) and (U2) are preferably 0.1 to 99% by weight and more preferably 30 to 95% by weight in the polyurethane resin (E). In addition, since the monofunctional polyurethane compound as described above has sufficient flexibility and excellent cured properties, it is preferable that such a compound is contained in an amount of 0.1 to 99% by weight. 30 to 95% by weight is more preferable.
The weight average molecular weights of the obtained polyurethane compounds (U1) and (U2) are preferably 2000 to 10,000, and more preferably 3000 to 7000.

The compound obtained by the first to third reactions of the present invention has a (meth) acryloyl group obtained by reacting the polyol compound (A or D) with all isocyanate groups of the polyisocyanate compound (B). No polyol compound (P1), obtained by further reacting the polyol compound (D) with all isocyanate groups of the compound obtained by reacting the polyisocyanate compound (B) obtained by the first reaction with the polyol compound (A). There may be a high molecular weight polyol compound (P2) having no (meth) acryloyl group. Since these compounds do not have a (meth) acryloyl group, they can exert a softening action. The polyol compound (P1) having no (meth) acryloyl group or the high molecular weight polyol compound (P2) having no (meth) acryloyl group preferably has a weight average molecular weight of 300 to 100,000, preferably 800 to 10, 000 is more preferable.
The polyol compound (P1) having no (meth) acryloyl group or the high molecular weight polyol compound (P2) having no (meth) acryloyl group is 0.1 to 99 in the obtained polyurethane resin (E). % By weight is preferable, and 1 to 20% by weight is more preferable.
Such a polyol compound (P1) having no (meth) acryloyl group or a high molecular weight polyol compound (P2) having no (meth) acryloyl group can impart high flexibility.

Further, among the compounds obtained by the first to third reactions of the present invention, a (meth) acrylate compound (C) having a hydroxyl group on all of the isocyanate groups of the polyisocyanate compound (B) is obtained. A compound (T1) having a plurality of (meth) acryloyl groups, an isocyanate group of the polyisocyanate compound (B) are linked by a polyol compound (A), and all of the terminal polyisocyanate compound (B) have a hydroxyl group (meth) acrylate There may also be a high molecular weight compound (T2) having a plurality of (meth) acryloyl groups obtained by reacting with the compound (C) to add a (meth) acryloyl group.
The content of the thus obtained high molecular weight compound (T1) having a plurality of (meth) acryloyl groups and compound (T2) having a plurality of (meth) acryloyl groups is 0.1 to The content is preferably 99% by weight, particularly preferably 1 to 20% by weight.

The third reaction of the present invention can also be carried out in the absence of a solvent. However, the product has a high viscosity and the above-described solvent and / or polymerizable compound (G) described later in the present invention for improving workability. It can also be performed under a mixture of The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. The aforementioned catalyst may be added for the purpose of shortening the reaction time.

The photosensitive resin composition of the present invention may contain the polyurethane resin (E) or the resin composition (F) of the present invention and a polymerizable compound (G) other than the components (E) or (F) as optional components. it can. Specific examples of the polymerizable compound (G) that can be used include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester.

Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (G-1); urethane (meth) acrylate (G-2). ); Epoxy (meth) acrylate (G-3); (poly) ether (meth) acrylate (G-4); alkyl (meth) acrylate or alkylene (meth) acrylate (G-5); having an aromatic ring (meth) ) Acrylate (G-6); (meth) acrylate (G-7) having an alicyclic structure, and the like, but are not limited thereto.
In addition, about a reaction material, it can obtain on well-known reaction conditions.

The (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention is a general term for (meth) acrylate having one or more ester bonds in the main chain. Acrylate (G-2) is a general term for (meth) acrylate having one or more urethane bonds in the main chain. Epoxy (meth) acrylate (G-3) is a monofunctional or higher functional epoxy compound and (meth). As a generic term for (meth) acrylate obtained by reacting acrylic acid, (poly) ether (meth) acrylate (G-4) is a generic term for (meth) acrylate having one or more ether bonds in the main chain, Alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) is a main chain having a straight chain alkyl, a branched alkyl, a straight chain or a halogen at the terminal. As a general term for (meth) acrylate which may have an atom and / or a hydroxyl group, (meth) acrylate (G-6) having an aromatic ring is (meth) acrylate having an aromatic ring in the main chain or side chain. As a general term, (meth) acrylate (G-7) having an alicyclic structure has an alicyclic structure that may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain (meth). These are used as a general term for acrylates.

Examples of the (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalate. Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) Acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; trimethylolpropane or glycerin 1 1 mole or more ε- caprolactone Le, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as δ- valerolactone mono-, di- or tri (meth) acrylate;

Mono-, di-, tri- or tetra (meth) acrylates of tetraols obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane Mono- or poly (meth) acrylate of hexaol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of dipentaerythritol;

Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, and maleic acid, fumaric acid, succinic acid Acids, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodiumsulfoisophthalic acid, and their reactants (Meth) acrylates of polyester polyols such as: (meth) acrylates of cyclic lactone-modified polyester diols composed of the diol components and polybasic acids and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Multifunctional (poly) ester ( Can be mentioned data) acrylate, and the like, but is not limited thereto.

The urethane (meth) acrylate (G-2) that can be used in combination with the photosensitive resin composition of the present invention includes at least one hydroxy compound (G-2-I) having an (meth) acryloyloxy group and an isocyanate compound (G- A general term for (meth) acrylates obtained by reaction with 2-ro).

Specific examples of the hydroxy compound (G-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy Ring-opening reaction of (meth) acrylate compounds having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone And the like.

Specific examples of the isocyanate compound (G-2-ro) include, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate. Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of isocyanate monomers or the above diisocyanates Things a trimer polyisocyanates of the isocyanate and the like; the and the isocyanate compound include polyisocyanates obtained by urethane reaction of the polyol compound.

In the reaction of the hydroxy compound (G-2-i) having a (meth) acryloyloxy group and the isocyanate compound (G-2-ro) when obtaining urethane (meth) acrylate, a polyol is optionally reacted. It doesn't matter.
Examples of polyols that can be used include those having 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Triols such as alkylene glycol, trimethylolpropane, pentaerythritol, alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, and the like; and these polyhydric alcohols and polybasic acids (for example, succinic acid) , Phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) polyester polyol obtained by reaction with polyhydric alcohol and ε-caprolactone Lactone alcohol, polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate) or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc.) Etc.

The epoxy (meth) acrylate (G-3) that can be used in combination with the photosensitive resin composition of the present invention is a (meth) acrylate obtained by reacting an epoxy resin containing one or more epoxy groups with (meth) acrylic acid. Is a general term. Specific examples of epoxy resins used as raw materials for epoxy (meth) acrylates include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy Bisphenol-type epoxy compounds such as resins, bisphenol-S type epoxy resins, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compounds; A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane Epoxy Hydrogenated bisphenol-type epoxy compounds such as compounds; Halogenated bisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl such as cyclohexanedimethanol diglycidyl ether compounds Ether compounds; aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether and diethylene glycol diglycidyl ether; polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether; phenol Novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadienephenol Epoxy resins, biphenol type epoxy resin, bisphenol -A novolac epoxy resins, naphthalene skeleton-containing epoxy resin, a heterocyclic epoxy resin or the like.

Examples of the (poly) ether (meth) acrylate (G-4) that can be used in combination with the photosensitive resin composition of the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. Functional (poly) ether (meth) acrylates;

Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymer, copolymer of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, polyhydric hydroxyl compound such as hydrogenated polybutadiene glycol and the like, and (meth) acrylic acid Induced polyfunctional (meth) acrylates; 1 mol or more of ethylene oxide, propylene oxide, butylene oxide per 1 mol of neopentyl glycol Di diol obtained by adding a cyclic ether (meth) acrylate;

Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; Hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S (Meth) acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of trimethylolpropane or glycerin;

Mono-, di-, tri-, or tetra (meth) acrylates of triols obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of pentaerythritol or ditrimethylolpropane; 1 mol of dipentaerythritol Examples thereof include polyfunctional (poly) ether (meth) acrylates such as hexaol tri- to hexafunctional (meth) acrylates to which cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide and the like are added in a molar amount or more.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) that can be used in combination with the photosensitive resin composition of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate Monofunctional (meth) acrylates such as

Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2 -Di (meth) acrylates of hydrocarbon diols of methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Triols such as acrylate or poly (meth) acrylate, mono- or poly (meth) acrylate of pentaerythritol, mono- or poly (meth) acrylate of ditrimethylolpropane, mono- or poly (meth) acrylate of dipentaerythritol, tetraol, hexa Mono- or poly (meth) acrylates of polyhydric alcohols such as oar;

And hydroxyl group-containing (meth) acrylic compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

Examples of the (meth) acrylate (G-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. And di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, but are not limited thereto.

Examples of the (meth) acrylate (G-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional (meth) acrylates having an alicyclic structure such as cyclopentenyl (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di ( Examples include polyfunctional (meth) acrylates having a cyclic structure such as (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate, It is not limited to these.

Examples of the compound having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate, in addition to the above-described compounds. Or a poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid; a (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanuric (meth) acrylates such as (meth) acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates, melamine (meth) acrylates, and the like can also be used.

Examples of the maleimide group-containing compound (G-8) that can be used in combination with the photosensitive resin composition of the present invention include Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2- Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate and N-ethyl- (2-maleimidoethyl) carbamate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene Aliphatic bismaleimides such as glycol-bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; cycloaliphatic such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Bismaleimide; with maleimidoacetic acid Esterification of various (poly) ols with carboxymaleimide derivatives such as maleimide compounds obtained by esterification with ritetramethylene glycol, maleimide compounds by esterification of maleimidocaproic acid with tetraethylene oxide adduct of pentaerythritol Although the (poly) ester (poly) maleimide compound etc. which can be obtained can be mentioned, it is not limited to these.

Examples of the (meth) acrylamide compound (G-9) that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; Examples thereof include polyfunctional (meth) acrylamides such as (meth) acrylamide.

Examples of the unsaturated polyester (G-10) that can be used in combination with the photosensitive resin composition of the present invention include fumaric acid esters such as dimethyl malate and diethyl malate; polyunsaturated such as maleic acid and fumaric acid. The esterification reaction product of carboxylic acid and a polyhydric alcohol can be mentioned.

The polymerizable compound (G) that can be used in combination with the photosensitive resin composition of the present invention is a combination of alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) that has low viscosity, excellent light resistance, and excellent workability. Although it is preferable, the compound is not limited to the above-described compounds, and one or a plurality of compounds can be used in combination without particular limitation as long as the compound has a copolymerizability with the component (E).
Among them, compounds having a (meth) acryloyloxy group having a long chain of C5 to C35, more preferably C15 to C35, such as alkyl (meth) acrylate or alkylene (meth) acrylate, are suitable. This is because a photosensitive resin composition having excellent compatibility and transparency can be obtained by having such a structure.

In the photosensitive resin composition of the present invention, the ratio of the components (E) and (G) is not particularly limited, but the component (G) is 10 to 2000 wt% with respect to 100 wt% of the component (E). %, Preferably 20 to 1000% by weight.

Specific examples of the photopolymerization initiator (H) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4 Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one; anthrax such as 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4 Benzophenones such as 2,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. The addition ratio of these is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

These can be used singly or as a mixture of two or more, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester Can be used in combination with an accelerator such as a benzoic acid derivative. As an addition amount of these accelerators, an amount of 100% by weight or less is added to the photopolymerization initiator (H) as necessary.

Furthermore, the photosensitive resin composition of the present invention is a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, an oxidation, depending on the application. Inhibitors, ultraviolet absorbers, flame retardants, pigments, dyes, and the like can be used as appropriate.

Specific examples of the non-reactive compound include a liquid or solid oligomer or resin having low reactivity or non-reactivity, and includes an alkyl (meth) acrylate copolymer, an epoxy resin, liquid polybutadiene, Cyclopentagen derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, phthalate esters, phosphate esters, Glycol esters, citric acid esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resin polyisoprene skeletons, oligomers or polymers having polybutadiene skeletons or xylene skeletons, and That d Ether product, homopolymer, epoxy-modified polybutadiene, butadiene - styrene random copolymer, polybutene, and the like can be mentioned softening agents etc., but is not limited thereto. The weight ratio of such components in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by 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, aluminum oxide, and glass. , Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon, and the like. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen group, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group.

Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, Nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like can be mentioned.

Examples of the silane coupling agent include silane coupling agents such as γ-glycidoxypropyltrimethoxysilane or γ-chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl), and the like. ) Titanate coupling agents such as phosphite titanate and bis (dioctylpyrophosphate) ethylene titanate; Aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; Zirconium coupling agents such as acetylacetone / zirconium complex, etc. be able to.

Any tackifier, antifoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant, pigment, and dye that can be used in the photosensitive resin composition of the present invention can be used. In the range which does not impair the sclerosis | hardenability and resin characteristic, a thing can be especially used without a restriction | limiting.

In order to obtain the photosensitive resin composition of the present invention, the above-described components may be mixed, and the order and method of mixing are not particularly limited.
When present in the composition of various additives, the weight ratio of the various additives in the photocurable transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and more preferably. Is 0.02 to 0.5% by weight.

The photosensitive resin composition of the present invention does not substantially require a solvent. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, benzene, toluene, xylene and the like It is also possible to dilute and use the photosensitive resin composition of the present invention with other generally used organic solvents such as aromatic hydrocarbons.

The photosensitive resin composition of the present invention can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm. Further, it can be cured by irradiation with energy rays other than ultraviolet rays or by heat.

Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short. Examples include arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.

The photosensitive resin composition of the present invention is excellent in flexibility, weather resistance and light resistance, and besides optical applications that need to maintain transparency, ink, plastic paint, paper printing, metal coating, furniture coating, etc. It is useful in various fields such as various coating fields, linings, adhesives, as well as insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants in the electronics field. More specific applications include planographic relief inks, flexographic inks, gravure inks, screen inks and other ink fields, glossy fields, paper coating materials fields, wood coating materials fields, beverage can coating materials or printing ink fields, Soft packaging film coating agent, printing ink or adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel type image display device It is useful for applications such as air gap fillers for display devices (fillers for gaps between display devices and face plates).

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

Synthesis example 1
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg · KOH / g) manufactured by Nippon Soda Co., Ltd. was used as a polyol compound. .88 g (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg · KOH / g) manufactured by Asahi Glass Co., Ltd. were charged and the internal temperature was 50 ° C. while stirring. did. Subsequently, 400.14 g (1.80 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 3.37 g of 4-methoxyphenol was added as a polymerization inhibitor and stirred until uniform, and 2-hydroxyethyl produced by Osaka Organic Chemical Industries, Ltd. as a (meth) acrylate compound having at least one hydroxyl group. 92.90 g (0.80 mol) of acrylate was added and reacted at 80 ° C. until the target NCO content was reached. Next, 3836.58 g (1.60 mol) of GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg · KOH / g) manufactured by Nippon Soda Co., Ltd. was used as the polyol compound, and tin octylate was used as the urethanization reaction catalyst. 2.02 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the reaction was terminated, and a resin composition (F-1) containing a polyurethane resin (E-1) was obtained. Obtained.

Synthesis example 2
2088.31 g of Nippon Soda Co., Ltd. G-2000 (polybutadiene polyol, hydroxyl value: 53.2 mg · KOH / g) as a polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg · KOH / g) manufactured by Asahi Glass Co., Ltd. was charged, and the internal temperature was adjusted to 50 ° C. while stirring. Subsequently, 400.14 g (1.80 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 3.00 g of 4-methoxyphenol as a polymerization inhibitor was added and stirred until uniform, and 2-hydroxyethyl produced by Osaka Organic Chemical Co., Ltd. as a (meth) acrylate compound having at least one hydroxyl group. 92.90 g (0.80 mol) of acrylate was added and reacted at 80 ° C. until the target NCO content was reached. Next, 3375.04 g (1.60 mol) of G-2000 (polybutadiene polyol, hydroxyl value: 53.2 mg · KOH / g) manufactured by Nippon Soda Co., Ltd. was used as the polyol compound, and tin octylate was used as the urethanization reaction catalyst. 80 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the reaction was terminated, and a resin composition (F-2) containing a polyurethane resin (E-2) was obtained. .

Synthesis example 3
1998.17 g of T-5652 (polycarbonate polyol, hydroxyl value: 55.6 mg · KOH / g) manufactured by Asahi Kasei Chemicals Corporation as a polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. (0.99 mol), 9.75 g (0.01 mol) of T-6001 (polycarbonate polyol, hydroxyl value: 115.1 mg · KOH / g) manufactured by Asahi Kasei Chemicals Co., Ltd., and the internal temperature was 50 ° C. while stirring. did. Subsequently, 400.14 g (1.80 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 2.87 g of 4-methoxyphenol as a polymerization inhibitor was added and stirred until uniform, and 2-hydroxyethyl produced by Osaka Organic Chemical Co., Ltd. as a (meth) acrylate compound having at least one hydroxyl group. 92.90 g (0.80 mol) of acrylate was added and reacted at 80 ° C. until the target NCO content was reached. Next, 3229.36 g (1.60 mol) of T-5552 (polycarbonate polyol, hydroxyl value: 55.6 mg · KOH / g) manufactured by Asahi Kasei Chemicals Co., Ltd. was used as the polyol compound, and tin octylate was used as the urethanization reaction catalyst. 72 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the reaction was terminated, and a resin composition (F-3) containing a polyurethane resin (E-3) was obtained. .

Synthesis example 4
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg · KOH / g) manufactured by Nippon Soda Co., Ltd. was used as a polyol compound. .88 g (0.99 mol), 31.26 g (0.01 mol) of Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg · KOH / g) manufactured by Asahi Glass Co., Ltd. as a polymerizable compound, Shin-Nakamura Chemical Co., Ltd. 133.86 g of S-1800A (isostearyl acrylate) manufactured and 2.00 g of 4-methoxyphenol as a polymerization inhibitor were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 333.45 g (1.50 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 58.06 g (0.50 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was added as a (meth) acrylate compound having at least one hydroxyl group, and the target NCO content was reached at 80 ° C. The reaction was continued until Next, 119.93 g (0.50 mol) of GI-2000 (hydrogenated polybutadiene polyol, hydroxyl value: 46.8 mg · KOH / g) manufactured by Nippon Soda Co., Ltd. was used as the polyol compound, and tin octylate was used as the urethanization reaction catalyst. 1.20 g was added, reacted at 80 ° C., and when the NCO content was 0.1% or less, the reaction was terminated, and a resin composition (F-4) containing a polyurethane resin (E-4) was obtained. Obtained.

Formulation Example 1
20 parts by mass of the resin composition (F-1) of Synthesis Example 1, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation Yasuhara Chemical Co., Ltd. Clearon M-105 (aromatic modified hydrogenated terpene resin) 18 parts by mass, JX Nippon Oil & Energy Corporation LV-100 (polybutene) 10 parts by mass, Nippon Soda Co., Ltd. GI- 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd. 4-HBA (4-hydroxybutyl acrylate) 3 parts by mass, LAMBSON Speed Cure TPO (2,4,6- 0.5 parts by mass of trimethylbenzoyldiphenylphosphine oxide) IRGACURE184 (1-hydroxycyclohexyl) manufactured by BASF 0.5 parts by mass of phenyl ketone) was heated to 70 ° C. and mixed to obtain a photosensitive resin composition of the present invention. The viscosity of this photosensitive resin composition was 3600 mPa · s.

Formulation Example 2
20 parts by mass of the resin composition (F-2) of Synthesis Example 2, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI- manufactured by Nippon Soda Co., Ltd. 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd. 4-HBA (4-hydroxybutyl acrylate) 3 parts by mass, LAMBSON Speed Cure TPO (2,4,6- 0.5 parts by mass of trimethylbenzoyldiphenylphosphine oxide) IRGACURE184 (1-hydroxycyclohexyl) manufactured by BASF 0.5 parts by mass of phenyl ketone) was heated to 70 ° C. and mixed to obtain a photosensitive resin composition of the present invention. The viscosity of this photosensitive resin composition was 3700 mPa · s.

Formulation Example 3
20 parts by mass of the resin composition (F-3) of Synthesis Example 3, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, T- manufactured by Asahi Kasei Chemicals Corporation 5652 (polycarbonate polyol) 20 parts by mass, Osaka Organic Chemical Co., Ltd. 4-HBA (4-hydroxybutyl acrylate) 3 parts by mass, Speed Cure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by LAMBSON ) 0.5 parts by mass, IRGACURE 184 (1-hydroxycyclohexyl phenyl) manufactured by BASF (Luketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a photosensitive resin composition of the present invention. The viscosity of this photosensitive resin composition was 3500 mPa · s.

Formulation Example 4
20 parts by mass of the resin composition (F-4) of Synthesis Example 4, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Bremer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI- manufactured by Nippon Soda Co., Ltd. 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Co., Ltd. 4-HBA (4-hydroxybutyl acrylate) 3 parts by mass, LAMBSON Speed Cure TPO (2,4,6- 0.5 parts by mass of trimethylbenzoyldiphenylphosphine oxide) IRGACURE184 (1-hydroxycyclohexyl) manufactured by BASF 0.5 parts by mass of phenyl ketone) was heated to 70 ° C. and mixed to obtain a photosensitive resin composition of the present invention. The viscosity of this photosensitive resin composition was 3000 mPa · s.

Formulation Examples 1 to 4 are shown in Table 1, and the following evaluation was performed.

(Viscosity) The viscosity was measured 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 with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(Curing shrinkage rate) Two 1 mm thick glass slides coated with a fluorine-based mold release agent were prepared, and the film thickness of the obtained ultraviolet curable resin composition was 200 μm on one mold release agent application surface. It applied so that it might become. Thereafter, the two slide glasses were bonded so that the respective release agent application surfaces face each other. The resin composition was cured by irradiating the resin composition with ultraviolet rays having an integrated light quantity of 3000 mJ / cm ^{2 through} a glass with a high-pressure mercury lamp (80 W / cm, ozone-less). Thereafter, the two slide glasses were peeled off to produce a cured product for measuring the film specific gravity. Based on JIS K7112 B method, specific gravity (DS) of hardened | cured material was measured. Moreover, the liquid specific gravity (DL) of the resin composition was measured at 25 degreeC. From the measurement results of DS and DL, the cure shrinkage percentage was calculated from the following formula and was less than 2.5%.
Curing shrinkage (%) = (DS−DL) ÷ DS × 100

(Rigidity) Two PET films subjected to a release treatment were prepared, and the obtained ultraviolet curable resin composition was applied to one of the release surfaces so that the film thickness was 200 μm. Thereafter, the two PET films were bonded together such that the release surfaces face each other. The resin composition was cured by irradiating the resin composition with ultraviolet rays having an integrated light quantity of 3000 mJ / cm ^{2 through} a PET film with a high-pressure mercury lamp (80 W / cm, ozone-less). Thereafter, the two PET films were peeled off to prepare a cured product for measuring the rigidity. The rigidity was measured with ARES (manufactured by TA Instruments).

(Transmittance) Two slide glasses having a thickness of 1 mm were prepared, and the obtained ultraviolet curable resin composition was applied to one of them so that the film thickness after curing was 200 μm. Then, two slide glasses were bonded together. The resin composition was cured by irradiating ultraviolet rays with an integrated light amount of 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less) through the glass to prepare a cured product for measuring transmittance. Regarding the transparency of the obtained cured product, the transmittance in the wavelength region of 400 to 800 nm and 400 to 450 nm was measured using a spectrophotometer (U-3310, Hitachi High-Technologies Corporation). As a result, the transmittance at 400 to 800 nm was 90% or more, and the transmittance at 400 to 450 nm was 90% or more.

(Heat and moisture resistant adhesion) A 1 mm thick glass slide and a 1 mm thick glass plate, or a 1 mm thick glass plate with a polarizing film pasted on one side, and an ultraviolet curable resin composition obtained on one side Was applied so that the film thickness was 200 μm, and the other was bonded to the coated surface. Through the glass, the resin composition was irradiated with ultraviolet rays having an integrated light amount of 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less), and the resin composition was cured to prepare a sample for evaluating adhesiveness. Using this, a heat resistance test at 85 ° C. and a humidity resistance test at 60 ° C. and 90% RH were conducted and left for 100 hours. In the sample for evaluation, peeling of the cured resin from the glass or polarizing film was confirmed visually, but there was no peeling.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

In addition, this application is based on the Japan patent application (2014-176040) for which it applied on August 29, 2014, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

The photosensitive resin composition containing the polyurethane compound of the present invention is excellent in flexibility, weather resistance, light resistance, and transparency, and thus is useful as an optical use member. Furthermore, the cured product of the photosensitive resin composition of the present invention is useful as an adhesive for bonding a transparent display substrate.

Claims

Compound (A), Compound (B), and Compound (C) shown below (number of moles of isocyanate group of compound (B))> (number of moles of hydroxyl group of compound (A) + number of hydroxyl groups of compound (C) The polyurethane resin (E) obtained by reacting in the relationship of the number of moles and then reacting with the compound (D).
Compound (A): Polyol compound compound (B): Polyisocyanate compound compound (C): (Meth) acrylate compound compound (D) having at least one hydroxyl group: Polyol compound
The polyurethane resin (E) according to claim 1, wherein the polyol compound (A) contains at least one polyol compound selected from hydrogenated polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol.
The polyurethane resin (E) according to claim 1 or 2, wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound.
The polyurethane resin (E) according to any one of claims 1 to 3, wherein the (meth) acrylate compound (C) having at least one hydroxyl group is 2-hydroxyethyl (meth) acrylate.
The polyurethane resin (E) according to any one of claims 1 to 4, wherein the polyol compound (D) contains at least one polyol compound selected from hydrogenated polybutadiene polyol, polybutadiene polyol, polyether polyol, and polycarbonate polyol. ).
Polyol compound (D) with respect to the number of moles of isocyanate groups remaining by (number of moles of isocyanate group of compound (B)) − (number of moles of hydroxyl group of compound (A) + number of moles of hydroxyl group of compound (C)) The polyol compound (D) is charged so that the number of moles of the hydroxyl group exceeds the number of remaining isocyanate groups, and the isocyanate group and the unreacted polyol compound (D) are contained as a plasticizer. A resin composition (F) containing the polyurethane resin (E) according to any one of the above.
A photosensitive resin composition comprising a polyurethane resin (E) according to any one of claims 1 to 5 or a resin composition (F) according to claim 6 and a polymerizable compound (G) other than (E). object.
The photosensitive resin composition according to claim 7, wherein the polymerizable compound (G) is alkyl (meth) acrylate or alkylene (meth) acrylate.
The photosensitive resin composition according to claim 7 or 8, comprising a photopolymerization initiator (H),
A cured product of the photosensitive resin composition according to any one of claims 7 to 9.