WO2017047612A1

WO2017047612A1 - Polyurethane compound and resin composition containing same

Info

Publication number: WO2017047612A1
Application number: PCT/JP2016/077048
Authority: WO
Inventors: 英照亀谷; 麻衣鍔本; 真之飯塚; 伸彦内藤; 貴文水口
Original assignee: 日本化薬株式会社
Priority date: 2015-09-18
Filing date: 2016-09-14
Publication date: 2017-03-23
Also published as: CN108026246A; TW201718684A; JP2017057349A; KR20180054560A

Abstract

Provided is a polyurethane compound having exceptional adhesiveness and flexibility as well as high weather resistance and light resistance, and being capable of maintaining transparency, it being possible to utilize the polyurethane compound in a resin composition particularly suited to use in optical applications. Provided are compound (A) and compound (B) shown below, and polyurethane compound (F) obtained by reacting compound (C) and compound (D). Compound (A): a hydrogenated polybutadiene polyol compound; compound (B): a polyisocyanate compound having trifunctional or higher isocyanate groups; compound (C): a diisocyanate compound; (D): a polyol compound; (E) a (meth)acrylate compound having at least one hydroxyl group.

Description

Polyurethane compound and resin composition containing the same

The present invention relates to a urethane (meth) acrylate (polyurethane compound) having a hydrogenated polybutadiene polyol as a main skeleton and a resin composition containing the same. 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, the hydrogenated polybutadiene polyol used has a relatively high iodine value, suggesting the possibility that it does not give properties that satisfy the currently required weather resistance and light resistance. Furthermore, since it is manufactured 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 estimated that the thing excellent in a softness | flexibility and the weather resistance and light resistance will be requested | required from now on. Patent Document 4 describes the application of urethane (meth) acrylate using a polyol compound having no aromatic ring to an LCD optical member.

In particular, in the bonding adhesive application of a capacitive touch panel, characterizing by utilizing the flexibility that is a characteristic of urethane (meth) acrylate is one of the mainstream techniques, for example, Patent Document 5 Also describes use examples of urethane (meth) acrylate. When used in such applications, the flexibility needs to be better, and it is necessary to apply urethane (meth) acrylate having a high molecular weight. However, when the molecular weight of urethane (meth) acrylate is usually increased, the flexibility can be improved, but the toughness tends to decrease, and as a result, the adhesive strength is generally decreased.

Japanese Patent No. 25582575 Japanese Patent No. 4868654 Japanese Unexamined Patent Publication No. 2012-46658 Japanese Unexamined Patent Publication No. 2011-190421 Japanese Unexamined Patent Publication No. 2015-67677

For optical member applications represented by these display applications, urethane (meth) acrylates require higher weather resistance, light resistance, improved cured film properties, and improved compatibility with other resins, monomers, and additives. Furthermore, in the case of touch panel adhesive applications, there is a demand for flexibility that affects the bonding condition and step following ability, and high adhesive strength that affects peeling.

The present invention improves the above requirements, provides a cured film excellent in weather resistance and light resistance, and excellent in flexibility, and can be used for a resin composition having a low shrinkage during curing and a high adhesive strength. An object of the present invention is to provide a polyurethane compound and a resin composition containing the polyurethane compound.

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 relates to the following (1) to (13).
(1) The polyurethane compound (F) which is a reaction product of the compound (A), the compound (B), the compound (C), the compound (D) and the compound (E) shown below.
Compound (A): Hydrogenated polybutadiene polyol compound compound (B): Polyisocyanate compound compound having a trifunctional or higher functional isocyanate group (C): Diisocyanate compound compound (D): Polyol compound compound (E) other than compound (A) The polyurethane compound (F) according to (1), wherein the iodine value of the (meth) acrylate compound (2) hydrogenated polybutadiene polyol compound (A) having at least one hydroxyl group is 20 or less.
(3) The polyurethane compound (F) according to any one of (1) and (2), wherein the polyisocyanate compound (B) having a trifunctional or higher functional isocyanate group mainly comprises a trimer of an aliphatic diisocyanate compound. ).
(4) The polyurethane compound (F) according to any one of (1) to (3), wherein the polyisocyanate compound (B) having a trifunctional or higher functional isocyanate group contains a trimer of hexamethylene diisocyanate as a main component.
(5) The polyurethane compound (F) according to any one of (1) to (4), wherein the diisocyanate compound (C) is an aliphatic diisocyanate compound.
(6) The polyurethane compound (F) according to any one of (1) to (5), wherein the polyol compound (D) has a number average molecular weight of 200 to 4,000.
(7) The polyurethane compound (F) according to any one of (1) to (6), wherein the (meth) acrylate compound (E) having at least one hydroxyl group is 2-hydroxyethyl (meth) acrylate.
(8) A photosensitive resin composition comprising the polyurethane compound (F) according to any one of (1) to (7) and a polymerizable compound (G) other than (F).
(9) The photosensitive resin composition according to (8), wherein the polymerizable compound (G) is alkyl (meth) acrylate or alkylene (meth) acrylate.
(10) The photosensitive resin composition according to (8) or (9), which contains a photopolymerization initiator (H).
(11) A cured product of the photosensitive resin composition according to any one of (8) to (10).
(12) The photosensitive resin composition according to any one of (8) to (10) for a filler for a gap between the display device and the surface plate,
(13) A touch panel comprising a cured product layer of the photosensitive resin composition according to (12).

The cured film of the photosensitive resin composition containing the polyurethane compound of the present invention has excellent substrate adhesion and flexibility, and high weather resistance and light resistance.

The polyurethane compound (F) of the present invention has a hydroxyl group of a hydrogenated polybutadiene polyol compound (A), a polyol compound (D), and a (meth) acrylate compound (E) having at least one hydroxyl group and a trifunctional or higher functional isocyanate group. It can be obtained by reacting the isocyanate groups of the polyisocyanate compound (B) and the diisocyanate compound (C). For example, a polyhydric polybutadiene polyol compound (A) and a polyol compound (D) can be obtained by reacting with a polyfunctional isocyanate group. First, the isocyanate compound (B) and the diisocyanate compound (C) are reacted (hereinafter referred to as the first reaction of the present invention), and then the (meth) acrylate compound (E) having at least one hydroxyl group with respect to the remaining isocyanate group. Reaction (hereinafter referred to as the present invention) Approach to called the second reaction) and the like.

As the hydrogenated polybutadiene polyol compound (A) used in the first reaction of the present invention, any hydrogenated reduction product of a general polybutadiene polyol can be used, but there are few residual double bonds particularly for optical applications. The iodine value is more preferably 20 or less, and particularly preferably 15 or less. In addition, as for the molecular weight of (A), all generally available molecular weight distributions can be used, but those having a number average molecular weight of 500 to 5000 are preferred particularly considering the balance between flexibility and curability, Those of 500 to 3000 are particularly preferred.
Commercially available hydrogenated polybutadiene polyol compounds (A) include, for example, Nippon Soda Co., Ltd .: GI-1000, GI-2000, GI-3000, CRAY VALLEY KRASOL HLBP-H 1000, HLBP-H 2000, HLBP- H 3000 etc. are mentioned.

Specific examples of the polyol compound (D) used in the first reaction of the present invention include, for example, polyether polyols such as polyethylene glycol, polybutylene glycol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, and polyethylene glycol adipate. Polyester polyols such as poly 1,4-butanediol adipate and polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentylglycol, cyclohexanedimethylol, hydrogenated bisphenol A, water Cycloaliphatic alcohols such as bisphenol F, spiro skeleton-containing alcohol, tricyclodecane dimethylol and pentacyclopentadecane dimethylol And alkylene oxide adducts thereof, branched or linear long chain alkyl diols such as hydrogenated polybutadiene diol, bisphenols such as bisphenol A and bisphenol F, and alkylene oxide adducts of bisphenol, trimethylolpropane, ditriol Examples thereof include polyols such as methylolpropane, pentaerythritol and dipentaerythritol, alkylene oxide adducts of these polyols, and polyester polyols obtained by reaction of these polyols with polybasic acids such as adipic acid. Although not particularly limited, it is particularly preferable to use polyether polyols in order to improve flexibility and compatibility in the cured product of the photosensitive resin composition using the polyurethane compound (F) of the present invention. Here, among the polyether polyols, polyethylene glycol and polypropylene glycol are preferable.
As for the molecular weight of such a polyol compound (D), all generally available molecular weight distributions can be used, but those having a number average molecular weight of 100 to 6000, particularly when the balance between flexibility and curability is achieved. And those of 200 to 4000 are particularly preferred.
In view of compatibility with other monomers while maintaining transparency and light resistance, the polyol compound (D) used particularly preferably is a polyether polyol having a molecular weight of 200 to 4000.

Here, in the present invention, when the hydrogenated polybutadiene polyol compound (A) and the polyol compound (D) are used in the reaction, the use ratio of the hydrogenated polybutadiene (A) and the polyol compound (D) is not particularly limited. Component A): Component (D) is preferably in a molar ratio of 9.999: 0.001 to 2: 8, more preferably 9.999: 0.001 to 3: 7, and 9.999: 0.001 to 4 : 6 is particularly preferable.

The polyisocyanate compound (B) having a trifunctional or higher functional isocyanate group used in the first reaction of the present invention is a compound containing three or more isocyanate groups in one molecule, for example, a trimer of hexamethylene diisocyanate. Examples of commercially available products include Duranate TPA-100 and TLA-100 manufactured by Asahi Kasei Chemicals. As a dimer of such a diisocyanate compound, a polyisocyanate compound having an alicyclic skeleton such as a trimer of isophorone diisocyanate can also be used. Examples of commercially available products include VESTANAT T1890 manufactured by Evonik. In addition, as a compound having three isocyanate groups in one molecule, an asymmetric isocyanate compound such as lysine ester triisocyanate can be used, and commercially available products include LTI manufactured by Kyowa Hakko. These may be used alone or in a mixture.
A polyisocyanate having a bifunctional isocyanate group such as a dimer of hexamethylene diisocyanate may be used together with the polyisocyanate compound having a trifunctional or higher functional isocyanate group. When using the said dimer together, it is preferable that it is 1/5 or less of the said trimer by area% of a peak in the measurement of a gel permeation chromatography, and it is more preferable that it is 1/10 or less.
<GPC measurement conditions>
Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC KF-802.5 (2) KF-802 KF-803
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

The diisocyanate compound (C) used in the first reaction of the present invention is a compound comprising two isocyanate groups in one molecule, such as an aliphatic diisocyanate compound and an aromatic diisocyanate compound. Etc. 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. The term “isocyanate compound” means a diisocyanate 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 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.

Examples of aromatic diisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene. Diisocyanate etc. are mentioned.

Among these, an aliphatic diisocyanate compound is preferable because the weather resistance of the coating film is improved. These may be used alone or in a mixture.

Here, in this invention, when the polyisocyanate compound (B) and diisocyanate compound (C) which have a trifunctional or more than trifunctional isocyanate group are used for reaction, the polyisocyanate compound (B) and diisocyanate which have a trifunctional or more than trifunctional isocyanate group are used. The ratio of the compound (C) used is not particularly limited, but the component (B) :( C) component is preferably 9: 1 to 0.01: 9.99, and 8: 2 to 0.1: 9. 9 is more preferable, and 7: 3 to 0.5: 9.5 is particularly preferable. It is because gelling can be effectively prevented by being in such a suitable range.

In the present invention, the first reaction is charged in an equivalent relationship ((B + C) / (A + D)> 1: [NCO] / [OH] molar ratio) such that isocyanate groups remain after the reaction. When the charging ratio is increased, a large amount of unreacted isocyanate compound is present, and when used in the photosensitive resin composition, the flexibility may be affected. On the other hand, when the preparation ratio is reduced, the molecular weight is increased and the curability of the photosensitive resin composition may be affected. Specifically, the OH group of the alcohol compound (A + D) is preferably 0.1 to 0.9 mol with respect to 1.0 mol of the NCO group of the isocyanate compound (B + C).

In the present invention, the first reaction can be carried out without solvent, but the viscosity of the product may increase. Therefore, in order to improve workability, it is preferable to carry out in the following solvent having no alcoholic hydroxyl group or in the polymerizable compound (G) described later. 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 diol compound (A + D) and the isocyanate compound (B + C).

The polyurethane compound (F) of the present invention is obtained by reacting (second reaction) a (meth) acrylate compound (E) having at least one hydroxyl group with respect to the remaining isocyanate group after the first reaction. be able to.

The (meth) acrylate compound (E) 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 at least one (meth) acryloyl group in one 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, polyester 2 such as lenglycol 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-caprolactone. 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 Polyfunctionals (meth) of tetrahydric or higher alcohols such as (meth) acrylate and ditrimethylolpropane hexa (meth) acrylate ) 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-described (meth) acrylate compound (E) having at least one hydroxyl group, 2-hydroxyethyl (meth) acrylate is particularly preferable 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 charged in an equivalent relationship such that the isocyanate group of the intermediate obtained after the first reaction is eliminated. Specifically, preferably, the OH group of the (meth) acrylate compound (E) having at least one hydroxyl group is 1.0 to 3.3 with respect to 1.0 mol of the NCO group of the intermediate obtained after the first reaction. The amount is 0 mol, more preferably 1.0 to 2.0 mol.

The second reaction of the present invention can also be carried out without solvent, but the viscosity of the product may increase. Therefore, in order to improve workability, it is preferably carried out in the above-described solvent and / or mixed with the polymerizable compound (G) described later in the present invention. 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.
Here, it is preferable to carry out under mixing with the polymerizable compound (G) described later. By using the compound as a diluent, the reaction system after completion of the second reaction becomes the photosensitive resin composition described below as it is, and most of the curable resin component occupies the photosensitive system. This is because the curable resin composition is less prone to problems during curing and adversely affects the cured properties. From the viewpoint of compatibility, the combined use of alkyl (meth) acrylate or alkylene (meth) acrylate (hereinafter referred to as G-5) is preferred.
Among them, compounds having a (meth) acryloyloxy group having a long chain of C4 to C34, more preferably C8 to C24, such as alkyl (meth) acrylate or alkylene (meth) acrylate, are suitable. This is because by having such a structure, a product having excellent compatibility and transparency can be obtained.

Usually, a polymerization inhibitor such as 4-methoxyphenol is already added to the 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 compound (F) of the present invention thus obtained is a residue obtained by the first reaction in which the hydroxyl group of the compound (A) has reacted with an isocyanate group or the hydroxyl group of the compound (D) is an isocyanate group. A terminal isocyanate group of a compound having a terminal residue is bonded to a residue obtained by reacting the isocyanate group of the compound (B) with a hydroxyl group or a residue obtained by reacting an isocyanate group of the compound (C) with a hydroxyl group. The residue which reacted with the hydroxyl group of the compound (E) and the residue obtained by reacting the hydroxyl group of the compound (E) with the terminal isocyanate group have a structure bonded via a urethane bond.
That is, as a specific example, a polyurethane compound having a structure in which the following formulas (A) to (C) are bonded via the reaction residues of the compound (B) and the compound (C).

(In the above formula (A), B represents a skeleton excluding the hydroxyl group of the hydrogenated polybutadiene polyol compound.)

(In the above formula (B), P represents a skeleton excluding the hydroxyl group of the polyol compound of component (D).)

(In the above formula (C), R represents a hydrogen atom or a methyl group.)

The photosensitive resin composition of the present invention can contain the polyurethane compound (F) of the present invention and a polymerizable compound (G) other than the component (F) as optional components. 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 It may be mentioned polyisocyanates obtained by urethanization reaction of the isocyanate compound and the polyol compound; compound of trimer polyisocyanates of the isocyanate and the like.

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 obtained by reacting an epoxy resin containing one or more functional epoxy groups with (meth) acrylic acid (meta). ) A general term for acrylate. 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 compounds such as hydrogenated polybutadiene glycol and other polyhydric hydroxyl compounds and (meth) acrylic Polyfunctional (meth) acrylates derived from acids; 1 mole or more of ethylene oxide, propylene oxide, butylene oxide, etc. per mole 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 thereof 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. However, it is not limited to these.

Moreover, as a compound which has the (meth) acryloyloxy group which can be used together with the photosensitive resin composition of this invention, reaction of a (meth) acrylic acid polymer and glycidyl (meth) acrylate other than an above-described compound, for example. Or poly (meth) acrylic polymer (meth) acrylate such as a reaction product of glycidyl (meth) acrylate polymer and (meth) acrylic acid; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanur (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 copolymerizability with the component (F).
Among them, compounds having a (meth) acryloyloxy group having a long chain of C4 to C34, more preferably C8 to C24, 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 (F) and (G) is not particularly limited, but the component (G) is 10 to 2000% by weight with respect to 100% by weight of the component (F). %, 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 Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide It is done. 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-glycidoxypropyl trelimethoxysilane and γ-chloropropyltrimethoxysilane, and tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl). ) 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 various additives are present in the composition, the weight ratio of the various additives in the photosensitive resin composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably 0.8%. 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 substrate adhesion, flexibility, weather resistance, high light resistance, in addition to optical applications that need to maintain transparency, ink, plastic paint, paper printing, It is useful in various coating fields such as metal coating and furniture painting, lining, adhesives, and many other fields such as insulating varnishes, insulating sheets, laminates, printed circuit 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
To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg · KOH) as a hydrogenated polybutadiene polyol compound / G) is 959.14 g (0.40 mol), Asahi Glass Co., Ltd. Excenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg · KOH / g) as a polyol compound is 312.59 g (0.10 mol), polymerizable 646.29 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. as a compound and 4.52 g of 4-methoxyphenol as a polymerization inhibitor were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. . Subsequently, 100.92 g (0.20 mol) of TLA-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was added as a polyisocyanate compound having a trifunctional or higher functional isocyanate group, and 88.92 g (0.40 mol) of isophorone diisocyanate was added as a diisocyanate compound. The reaction was allowed to reach the target NCO content at 80 ° C. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was used as the (meth) acrylate compound having at least one hydroxyl group, and 0 octylate tin was used as the urethanization reaction catalyst. .45 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the end point of the reaction was taken to obtain a polyurethane compound (F-1).

Synthesis example 2
GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 67.2 mg · KOH) as a hydrogenated polybutadiene polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. / G) is 667.98 g (0.40 mol), Exenol 1020 (polypropylene glycol, hydroxyl value: 111 mg · KOH / g) manufactured by Asahi Glass Co., Ltd. as a polyol compound is used as a polymerizable compound. 335.12 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. and 3.02 g of 4-methoxyphenol as a polymerization inhibitor were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 100.92 g (0.20 mol) of TLA-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was added as a polyisocyanate compound having a trifunctional or higher functional isocyanate group, and 88.92 g (0.40 mol) of isophorone diisocyanate was added as a diisocyanate compound. The reaction was allowed to reach the target NCO content at 80 ° C. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was used as the (meth) acrylate compound having at least one hydroxyl group, and 0 octylate tin was used as the urethanization reaction catalyst. .30 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the end point of the reaction was taken to obtain a polyurethane compound (F-2).

Synthesis example 3
GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 67.2 mg · KOH) as a hydrogenated polybutadiene polyol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. / G) 75.47 g (0.45 mol), NOF Corporation PEG # 400 (polyethylene glycol, hydroxyl value: 278 mg · KOH / g) as a polyol compound, polymerizable 335.98 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. as a compound and 3.02 g of 4-methoxyphenol as a polymerization inhibitor were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. . Subsequently, 100.92 g (0.20 mol) of TLA-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was added as a polyisocyanate compound having a trifunctional or higher functional isocyanate group, and 88.92 g (0.40 mol) of isophorone diisocyanate was added as a diisocyanate compound. The reaction was allowed to reach the target NCO content at 80 ° C. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was used as the (meth) acrylate compound having at least one hydroxyl group, and 0 octylate tin was used as the urethanization reaction catalyst. .30 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the end point of the reaction was taken to obtain a polyurethane compound (F-3).

Comparative Synthesis Example 1
To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, GI-2000 manufactured by Nippon Soda Co., Ltd. (iodine value: 12.2, hydroxyl value: 46.8 mg · KOH) as a hydrogenated polybutadiene polyol compound / G) 959.14 g (0.40 mol), NOF Corporation PEG # 400 (polyethylene glycol, hydroxyl value: 278 mg · KOH / g) as a polyol compound, 40.37 g (0.10 mol), polymerizable 400.52 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. as a compound and 3.60 g of 4-methoxyphenol as a polymerization inhibitor were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. . Subsequently, 155.61 g (0.70 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. was used as the (meth) acrylate compound having at least one hydroxyl group, and 0 octylate tin was used as the urethanization reaction catalyst. .36 g was added and reacted at 80 ° C., and when the NCO content was 0.1% or less, the end point of the reaction was taken to obtain a polyurethane compound (U-1).

Formulation Example 1
20 parts by mass of the polyurethane compound (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, 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-2000 manufactured by Nippon Soda Co., Ltd. (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-trimethyl) 0.5 parts by mass of benzoyldiphenylphosphine oxide), IRGACURE184 (1-hydroxycyclo) manufactured by BASF Hexylphenylketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 4500 mPa · s.

Formulation Example 2
20 parts by mass of the polyurethane compound (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-2000 manufactured by Nippon Soda Co., Ltd. (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-trimethyl) 0.5 parts by mass of benzoyldiphenylphosphine oxide), IRGACURE184 (1-hydroxycyclo) manufactured by BASF Hexylphenylketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 4000 mPa · s.

Formulation Example 3
20 parts by mass of the polyurethane compound (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, GI-2000 manufactured by Nippon Soda Co., Ltd. (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-trimethyl) 0.5 parts by mass of benzoyldiphenylphosphine oxide), IRGACURE184 (1-hydroxycyclo) manufactured by BASF Hexylphenylketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 4100 mPa · s.

Comparative formulation example 1
20 parts by mass of the polyurethane compound (U-1) of Comparative 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 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-hydroxysilane) manufactured by BASF Chlohexyl phenyl ketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 3500 mPa · s.

Formulation Examples 1 to 3 and Comparative Formulation Example 1 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) Prepare 2 pieces of 1 mm-thick slide glass coated with a fluorine-based release agent, and on one of the release agent-coated surfaces, the obtained photosensitive resin composition (ultraviolet curable resin composition) (Also referred to as a product) was applied so that the film thickness was 200 μm. 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 rate was calculated from the following formula.
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 visually confirmed, and adhesiveness was evaluated according to the following evaluation criteria.
◎ ・・・ No peeling ○ ・・・ Slight peeling like unevenness △ ・・・ Partial peeling ×× 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 (2015-185385) for which it applied on September 18, 2015, 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 useful as an optical member because it is excellent in adhesiveness and flexibility, weather resistance, light resistance, and transparency. 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

A polyurethane compound (F) which is a reaction product of the compound (A), the compound (B), the compound (C), the compound (D) and the compound (E) shown below.
Compound (A): Hydrogenated polybutadiene polyol compound compound (B): Polyisocyanate compound compound having a trifunctional or higher functional isocyanate group (C): Diisocyanate compound compound (D): Polyol compound compound (E) other than compound (A) : (Meth) acrylate compound having at least one hydroxyl group
The polyurethane compound (F) according to claim 1, wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less.
The polyurethane compound (F) according to any one of claims 1 and 2, wherein the polyisocyanate compound (B) having a tri- or higher functional isocyanate group mainly comprises a trimer of an aliphatic diisocyanate compound.
The polyurethane compound (F) according to any one of claims 1 to 3, wherein the polyisocyanate compound (B) having a trifunctional or higher functional isocyanate group mainly comprises a trimer of hexamethylene diisocyanate.
The polyurethane compound (F) according to any one of claims 1 to 4, wherein the diisocyanate compound (C) is an aliphatic diisocyanate compound.
The polyurethane compound (F) according to any one of claims 1 to 5, wherein the polyol compound (D) has a number average molecular weight of 200 to 4,000.
The polyurethane compound (F) according to any one of claims 1 to 6, wherein the (meth) acrylate compound (E) having at least one hydroxyl group is 2-hydroxyethyl (meth) acrylate.
A photosensitive resin composition comprising the polyurethane compound (F) according to any one of claims 1 to 7 and a polymerizable compound (G) other than (F).
The photosensitive resin composition according to claim 8, wherein the polymerizable compound (G) is alkyl (meth) acrylate or alkylene (meth) acrylate.
The photosensitive resin composition of Claim 8 or 9 containing a photoinitiator (H).
A cured product of the photosensitive resin composition according to any one of claims 8 to 10.
The photosensitive resin composition according to any one of claims 8 to 10, which is used as a filler for a gap between the display device and the surface plate.
A touch panel comprising a cured product layer of the photosensitive resin composition according to claim 12.