CN105916907A - Polyurethane compound and resin composition containing same, cured product of said resin composition, and method for producing said resin composition - Google Patents
Polyurethane compound and resin composition containing same, cured product of said resin composition, and method for producing said resin composition Download PDFInfo
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- CN105916907A CN105916907A CN201580004580.4A CN201580004580A CN105916907A CN 105916907 A CN105916907 A CN 105916907A CN 201580004580 A CN201580004580 A CN 201580004580A CN 105916907 A CN105916907 A CN 105916907A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Provided are: a polyurethane compound which enables the preparation of a resin composition that can be cured into a cured film having excellent weather resistance and light resistance and also having excellent flexibility and can also exhibit a low degree of shrinkage upon the curing; a resin composition containing the polyurethane compound; a cured product of the resin composition; and a method for producing the resin composition. The polyurethane compound can be produced by reacting a hydrogenated polybutadiene polyol compound (A), polyethylene glycol (B), a polyisocyanate compound (C) and a (meth)acrylate compound having at least one hydroxy group (D) together.
Description
Technical field
The present invention relates to the carbamate (first with hydrogenated butadiene polymer polyhydric alcohol as main skeleton
Base) acrylate, resin combination etc. containing this carbamate (methyl) acrylate.This
Outward, the flexibility of the cured film of the resin combination of the present invention, the transparency, moisture-proof, to base
The adhesiveness of material is excellent, and cure shrinkage is also few, therefore especially as the optics of display equipment
The laminating purposes of film etc. and useful.
Background technology
Since Yi Wang, as polyol compound and polyisocyanate compound and containing hydroxyl
Carbamate (methyl) acrylate of the product of (methyl) acrylate compounds is used as more
The purposes such as smears, adhesive, photoresist.Such as special as patent documentation 1
It is not in the field that the deterioration that optical applications etc. is caused by xanthochromia becomes problem, high with the transparency
Carbamate is designed based on the polyisocyanates of polyol compound and aliphatic or ester ring type
(methyl) acrylate compounds.
Additionally, as being exposed to changing of xanthochromia in the case of harsh conditions or weatherability
Kind, selective hydrogenation polybutadiene makes polyol compound to have given play to advantage sometimes.In patent
In document 2, hydrogenated butadiene polymer polyhydric alcohol is used to manufacture carbamate (methyl) acrylate.
Think: as solidfied material, have excellent weather resistance, but as hydrogenated butadiene polymer skeleton, hydrophobicity
The highest, with as the monomer that can coordinate in compositions, additive the compatibility in terms of
Exist and limit.It addition, the iodine number of the hydrogenated butadiene polymer polyhydric alcohol used is higher, suggesting can
Can not give and meet the weatherability currently required that, sunproof characteristic.Additionally, as amino first
The resin of acid esters (methyl) acrylate manufactures in the way of without dilution, therefore in actual industrialization
Time, it is possible to viscosity is high and goes wrong in terms of workability.
In recent years, carbamate (methyl) acrylate is in LCD (liquid crystal display) purposes
Research, practical the most prevailing.Such as in patent documentation 3, as employing polybutadiene (first
Base) the showing at optics of acrylate oligomer and carbamate (methyl) acrylate oligomer
In the laminating of body or touch sensor use light-cured type adhesive compound and be employed.Make
For carbamate (methyl) acrylate, thus it is speculated that the most also require flexibility excellent and weatherability,
Light resistance higher carbamate (methyl) acrylate.It addition, described in patent documentation 4
Employ carbamate (methyl) acrylate of the polyol compound not having aromatic ring
Application in LCD optical component.
Prior art literature
Patent documentation
Patent documentation 1: No. 2582575 publications of Japanese Patent No.
Patent documentation 2: No. 4868654 publications of Japanese Patent No.
Patent documentation 3: Japanese Unexamined Patent Publication 2012-46658 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-190421 publication
Summary of the invention
Invent problem to be solved
As representative optical component purposes such as display applications, for carbamate (methyl)
Acrylate require higher weatherability, light resistance and improve cured film physical property, improvement and its
Its resin, monomer class and the compatibility of additive, additionally, when industrialization, it is contemplated that actual
Production line, the most also require carbamate (methyl) acrylate material excellent to workability and
The detailed design of compositions.
It is an object of the invention to improve above-mentioned requirements, it is provided that urethanes, containing this gather
The resin combination of urethane compound, the solidfied material of this resin combination and this resin combination
Manufacture method, described urethanes can provide a kind of resin combination, described resin group
When compound provides weatherability, excellent in light-resistance and the cured film of flexibility excellence and solidifies
Shrinkage factor low.
Means for solving the above
The present inventor, in order to solve the problems referred to above, conducts in-depth research, it was found that have
The resin combination of specific compound and composition solves the problems referred to above, thus completes the present invention.
That is, the present invention relates to:
(1) a kind of urethanes (E), it is by making following shown compound (A), chemical combination
Thing (B), compound (C) and compound (D) react and obtain,
Compound (A): hydrogenated butadiene polymer polyol compound
Compound (B): Polyethylene Glycol
Compound (C): polyisocyanate compound
Compound (D): there is (methyl) acrylate compounds of more than 1 hydroxyl；
(2) urethanes (E) as described in (1), wherein, the polynary alcoholization of hydrogenated butadiene polymer
The iodine number of compound (A) is less than 20；
(3) urethanes (E) as described in (1) or (2), wherein, the number of Polyethylene Glycol (B) is equal
Molecular weight is 100～4,000；
(4) urethanes (E) as according to any one of (1)～(3), wherein, polyisocyanic acid
Ester compounds (C) is aliphatic category diisocyanate cpd；
(5) urethanes (E) as according to any one of (1)～(4), wherein, has 1
(methyl) acrylate compounds (D) of above hydroxyl is (methyl) acrylic acid 2-hydroxy methacrylate；
(6) a kind of photosensitive polymer combination, it is characterised in that described photosensitive polymer combination
Containing the urethanes (E) according to any one of (1)～(5) and the polymerizable in addition to (E)
Compound (F)；
(7) photosensitive polymer combination as described in (6), wherein, polymerizable compound (F) is (first
Base) alkyl acrylate or (methyl) acrylic acid alkylene ester；
(8) photosensitive polymer combination as described in (6) or (7), it contains Photoepolymerizationinitiater initiater
(G)；
(9) a kind of solidfied material, its photosensitive polymer combination according to any one of (6)～(8)
Solidfied material；
(10) manufacture method of a kind of photosensitive polymer combination described in (6) or (7), its feature exists
In, synthesis of polyurethane compound (E) in the presence of polymerizable compound (F).
Invention effect
The softness of the cured film of the photosensitive polymer combination of the urethanes containing the present invention
Property excellent, weatherability, light resistance are high, in addition to needing to keep the optical applications of the transparency,
The application etc. that can also be applied to ink, plastic paint, paper printing, metal coated, furniture is each
Kind of coating applications, lining, adhesive and the insulating varnish in electronic applications, insulating trip,
Multiple fields such as plywood, printed base plate, resist ink (resist ink), semiconductor encapsulant.
Detailed description of the invention
The urethanes (E) of the present invention is characterised by, first makes hydrogenated butadiene polymer polynary
Alcohol (A), Polyethylene Glycol (B) and polyisocyanate compound (C) reaction (the hereinafter referred to as first reaction),
Then, the isocyanide of (methyl) acrylate compounds (D) with more than 1 hydroxyl and residual is made
Perester radical reaction (the hereinafter referred to as second reaction).
As the hydrogenated butadiene polymer polyhydric alcohol (A) used in first reaction of the present invention, if
It is that the hydro-reduction product of common polybutadiene polyol just can use, especially with respect to light
Learn purposes and preferably remain the hydrogenated butadiene polymer polyhydric alcohol that double bond is few, be more preferably 20 as iodine number
Hereinafter, particularly preferably less than 15.It addition, about the molecular weight of (A), usually obtain
The hydrogenated butadiene polymer polyhydric alcohol of molecular weight distribution all can use, especially obtain flexibility with
In the case of the balance of curable, preferred number average molecular weight is the hydrogenation polybutadiene of 500～5000
Alkene polyhydric alcohol, particularly preferred number-average molecular weight are the hydrogenated butadiene polymer polyhydric alcohol of 500～3000.
As commercially available hydrogenated butadiene polymer polyhydric alcohol (A), can enumerate such as: Japan's Cao Da strain
The KRASOL that the GI-1000 of formula commercial firm manufacture, GI-2000, GI-3000, Cray Willie manufacture
HLBP-H 1000, HLBP-H 2000, HLBP-H 3000 etc..
As the concrete example of the Polyethylene Glycol (B) used in first reaction of the present invention, generally
Commercially available Polyethylene Glycol all can use, it is also possible to uses such as Japan Oil Co to manufacture
PEG#200T、PEG#200、PEG#300、PEG#400、PEG#600、PEG#1000、
PEG#1500、PEG#1540、PEG#200、PEG#4000、PEG#4000P、PEG#6000、
PEG#6000P, PEG#11000, PEG#20000 etc. or their ammonia through moisture regulation
Carbamate grade etc..As water quantities, the thickening caused for the increase of Inhibitory molecules amount,
It is preferably less than 2%, particularly preferably less than 1%.
It addition, about the molecular weight of (B), (B) of the molecular weight distribution usually obtained is the most permissible
Use, especially in the case of obtaining the flexibility balance with curable, preferred number average molecular weight
Being (B) of 50～6000, particularly preferred number-average molecular weight is (B) of 100～4000.
Here, in obtained urethanes (E), from by including autohemagglutination dispersedly in
The structure of ethylene glycol and include polyethylene glycol backbone and hydrogenated butadiene polymer skeleton equably in thus
From the viewpoint of improving the compatibility with monomer, the number-average molecular weight of Polyethylene Glycol is more preferably
Less than 2000, particularly preferably less than 500.
It addition, in urethanes (E), from hydrogenated butadiene polymer polyhydric alcohol (A) and poly-second two
From the point of view of the total molal quantity of alcohol (B), preferably include the Polyethylene Glycol (B) of 5～10 moles of % in.
Hydroxyl value is preferably less than 400, and more preferably less than 300.Lower limit is not particularly limited,
For example, more than 50 both may be used.
Here, in the present application, by hydrogenated butadiene polymer polyhydric alcohol (A) and Polyethylene Glycol (B)
During for reacting, the usage rate of hydrogenated butadiene polymer (A) and Polyethylene Glycol (B) limits the most especially
Fixed, (A) composition: (B) composition is preferably 9.999:0.001～1:9 with molar ratio computing, more preferably
For 9.999:0.001～3:7, particularly preferably 9.999:0.001～4:6.
It addition, about the equal molecule of number of the hydrogenated butadiene polymer polyhydric alcohol (A) used in the present invention
Amount, preferred compositions uses the number bigger than the number-average molecular weight of the Polyethylene Glycol (B) used to divide equally
Son amount, more preferably hydrogenated butadiene polymer polyhydric alcohol (A) has the number-average molecular weight of Polyethylene Glycol (B)
The number-average molecular weight of+500, particularly preferred hydrogenated butadiene polymer polyhydric alcohol (A) has Polyethylene Glycol (B)
The number-average molecular weight of number-average molecular weight+1000.
The polyisocyanate compound (C) used in first reaction of the present invention is in 1 molecule
Containing the compound of more than 2 NCOs, can enumerate such as: aliphatic category two isocyanide
Ester compound, fragrance same clan diisocyanate cpd, their trimer etc..This institute
The aliphatic category diisocyanate cpd said refers to what NCO was bonded with chain carbon atoms
Diisocyanate cpd and NCO are different with the two of the carbon atom bonding of cyclic saturated hydrocarbon
Cyanate esters, fragrance same clan diisocyanate cpd refers to NCO and aromatic rings
The isocyanate compound of carbon atom bonding.
As aliphatic category diisocyanate cpd, can enumerate such as: 1,6-hexa-methylene two
Isocyanates, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenation of benzene two are sub-
Methyl diisocyanate, hydrogenated diphenyl methane diisocyanate, hexamethylene-1,3-diisocyanate,
Hexamethylene-1,4-diisocyanate, dicyclohexyl methyl hydride-4,4 '-diisocyanate, between tetramethyl two
Toluene di-isocyanate(TDI), tetramethyl xylol diisocyanate, 1,4-tetramethylene two Carbimide.
Ester, 1,12-ten dimethylene diisocyanate, 2,2,4-trimethyl-cyclohexane diisocyanate, 2,4,4-
Trimethyl-cyclohexane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-
Trimethyl hexamethylene diisocyanate, lysinediisocyanate, norbornane two Carbimide.
Ester etc..
As fragrance same clan diisocyanate cpd, can enumerate such as: toluene diisocynate
Ester, XDI, methyl diphenylene diisocyanate, 1,5-naphthalene two Carbimide.
Ester, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,6-
The diisocyanate monomer classes etc. such as phenylene diisocyanate.
Wherein, aliphatic category diisocyanate cpd and this aliphatic category diisocyanate chemical combination
The trimer of thing makes the weatherability of film well, the most preferably.As aliphatic category two Carbimide.
The trimer of ester compounds, can enumerate such as: the isocyanide of above-mentioned aliphatic category isocyanates
Urea acid esters type polyisocyanates etc., specifically, can enumerate hexamethylene diisocyanate,
Isophorone diisocyanate etc..They can each be used alone, or uses with mixture.
In the present invention, the first reaction is with the equivalent relation (C/ (A of residual isocyanate base after the reaction
+ B) ＞ 1:[NCO]/[OH] mol ratio) feed intake.When improving rate of charge, unreacted many
Isocyanate compound (C) exists in a large number, sometimes causes the flexibility of photosensitive polymer combination
Impact.During it addition, reduce rate of charge, molecular weight improves, sometimes to photosensitive polymer combination
Curable impact.Specifically, it is preferably: relative to polyisocyanate compound (C)
NCO base 1.0mol, the OH base of alcoholic compound (A+B) is set as 0.1～0.9mol.
In the present invention, the first reaction can be carried out under solvent-free, but due to the viscosity of product
High and in order to improve workability, preferably do not have in the solvent of alcohol hydroxyl group or rear following
The polymerizable compound (F) stated is carried out.As the concrete example of solvent, can acetone, first and second
The virtues such as the ketones such as ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, benzene,toluene,xylene, durene
Fragrant race hydro carbons, glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropyl two
The glycol ethers such as diethylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether, ethyl acetate,
Butyl acetate, methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetic acid
Ester, carbitol acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate,
Dipropylene glycol monomethyl ether acetas, dialkyl glutarate, dialkyl succinate, adipic acid
The ring-type esters of esters, the gamma-butyrolactons etc. such as dialkyl, petroleum ether, Petroleum, hydrogenated naphtha,
The single organic solvent such as petroleum solvents such as solvent naphtha or mixed organic solvents are carried out.
Reaction temperature is usually 30～150 DEG C, preferably in the range of 50～100 DEG C.Reaction
Terminal confirms with the minimizing of amount of isocyanate.It addition, with shorten them response time as mesh
, catalyst can be added.As this catalyst, it is possible to use base catalyst and acidity are urged
Any one in agent.As the example of base catalyst, can enumerate pyridine, pyrroles, three
The phosphine classes such as the amines such as ethamine, diethylamine, dibutyl amine, ammonia, tributylphosphine, triphenylphosphine.Separately
Outward, as the example of acidic catalyst, copper naphthenate, cobalt naphthenate, aphthenic acids can be enumerated
Zinc, aluminium butoxide, tetraisopropyl titanate, tetrabutyl zirconate, aluminum chloride, tin octoate, three
The lewis acid catalysts such as lauric acid tin octylate, dibutyl tin laurate, octyltin diacetate.
The addition of these catalyst is relative to diatomic alcohol compounds (A+B) and polyisocyanate compound
(C) total weight parts 100 weight portion is usually 0.1～1 weight portion.
After the urethanes (E) of the present invention can be by reacting first, then make have 1
(methyl) acrylate compounds (D) of individual above hydroxyl reacts (second with the NCO of residual
Reaction) and obtain.
(methyl) acrylic acid with more than 1 hydroxyl used in second reaction of the present invention
Ester compounds (D) refers to have at least one hydroxyl and at least one (methyl) propylene in 1 molecule
The compound of perester radical, specifically, can enumerate: (methyl) acrylic acid 2-hydroxy methacrylate, third
Glycol list (methyl) acrylate, butanediol list (methyl) acrylate, pentanediol list (methyl) third
Olefin(e) acid ester, hexanediol list (methyl) acrylate, diethylene glycol list (methyl) acrylate, dipropyl
Glycol list (methyl) acrylate, triethylene glycol list (methyl) acrylate, tripropylene glycol list (methyl)
Acrylate, TEG list (methyl) acrylate, polyethyleneglycol (methyl) acrylate,
Polypropylene glycol list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, ethoxyquin new penta
Glycol list (methyl) acrylate, 3-hydroxypivalic acid DOPCP list (methyl) acrylate etc. two
List (methyl) acrylate of unit's alcohol；
Trimethylolpropane list (methyl) acrylate, ethoxyquin trimethylolpropane list (methyl) third
Olefin(e) acid ester, the third oxidation trimethylolpropane list (methyl) acrylate, isocyanuric acid three (2-hydroxyl second
Base) ester list (methyl) acrylate, glycerol list (methyl) acrylate, trimethylolpropane two (first
Base) acrylate, ethoxyquin trimethylolpropane two (methyl) acrylate, third oxidation three hydroxyl first
Base propane two (methyl) acrylate, isocyanuric acid three (2-hydroxyethyl) ester two (methyl) acrylic acid
List (methyl) acrylate of the trihydroxylic alcohols such as ester, glycerol two (methyl) acrylate and two (methyl) third
Olefin(e) acid ester or by list (first modified to the part alkyl of the hydroxyl of these alcohol or 6-caprolactone
Base) acrylate and two (methyl) acrylate；
Tetramethylolmethane list (methyl) acrylate, dipentaerythritol list (methyl) acrylate, double three
Hydroxymethyl-propane list (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, two seasons penta 4
Alcohol two (methyl) acrylate, double trimethylolpropane two (methyl) acrylate, tetramethylolmethane three
(methyl) acrylate, dipentaerythritol three (methyl) acrylate, double trimethylolpropane three (first
Base) acrylate, dipentaerythritol four (methyl) acrylate, double trimethylolpropane four (methyl)
Acrylate, dipentaerythritol six (methyl) acrylate, double trimethylolpropane six (methyl) third
Multifunctional (methyl) acrylate with hydroxyl of the alcohol more than quaternarys such as olefin(e) acid ester or by these
The part alkyl of the hydroxyl of alcohol or modified multifunctional (methyl) with hydroxyl of 6-caprolactone
Acrylate；Deng.
Among above-mentioned (methyl) acrylate compounds (D) with more than 1 hydroxyl, from solid
From the viewpoint of the property changed and flexibility excellence, particularly preferably (methyl) acrylic acid 2-hydroxy methacrylate.From
From the viewpoint of workability is easy, polymerizable described later in the present invention can be added when reaction
Compound (F).
Second reaction of the present invention is can make the isocyanates of intermediate obtained after the first reaction
The equivalent relation that base exhausts feeds intake.Specifically, it is preferably: relative in the first reaction
After the NCO base 1.0mol of intermediate that obtains, will have (methyl) propylene of more than 1 hydroxyl
The OH base of ester compound (D) is set as 1.0～3.0mol, be further preferably set as 1.0～
2.0mol。
Second reaction of the present invention can also be carried out under solvent-free, but due to the viscosity of product
High and in order to improve workability, preferably in above-mentioned solvent and/or aftermentioned with the present invention
Polymerizable compound (F) mixing under carry out.It addition, reaction temperature be usually 30～150 DEG C,
Preferably in the range of 50～100 DEG C.The terminal of reaction confirms with the minimizing of amount of isocyanate.
For the purpose of shortening the above-mentioned response time, above-mentioned catalyst can be added.
Here, preferably carrying out under the mixing of polymerizable compound described later (F).This is because,
By this compound is occupied major part as diluent, curable resin composition, therefore solid
It is not likely to produce unfavorable condition during change, and is difficult to solidification physical property is produced harmful effect.It addition,
From the viewpoint of the compatibility, preferably and sub-with (methyl) alkyl acrylate or (methyl) acrylic acid
Arrcostab (following F-5).
Wherein, preferably: for (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester etc. and
Have C5～C35, more preferably C15～C35 long-chain there is (methyl) acryloxy
Compound.This is because, by having a structure in which, the compatibility and the transparency can be obtained
Excellent material.
As in the acrylate compounds of raw material, with the addition of 4-methoxyphenol etc.
Polymerization inhibitor, but can also again add polymerization inhibitor when reaction.As such polymerization inhibitor
Example, can enumerate hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butyl phenol,
2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, 1,4-benzoquinone, 2,5-dihydroxy 1,4-benzoquinone, fen
Thiazine etc..Its usage amount is 0.01～1 weight % relative to reacting material mixture.
The photosensitive polymer combination of the present invention can be containing the urethanes (E) of the present invention
(E) polymerizable compound (F) beyond composition is as optional member.As gathering of can using
The concrete example of polymerisable compounds (F), can enumerate and have the compound of (methyl) acryloxy, maleoyl
Group with imine moiety, (methyl) acrylamide compound, unsaturated polyester (UP) etc..
As having (methyl) propylene in the photosensitive polymer combination of the present invention
The concrete example of the compound of acyloxy, can enumerate (gathering) ester (methyl) acrylate (F-1)；Amino
Formic acid esters (methyl) acrylate (F-2)；Epoxy (methyl) acrylate (F-3)；(gathering) ether (methyl)
Acrylate (F-4)；(methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester (F-5)；Tool
There is (methyl) acrylate (F-6) of aromatic rings；There is (methyl) acrylate (F-7) of alicyclic structure
Deng, but it is not limited to these.
It should be noted that about product, can obtain under known reaction condition.
Can (gathering) ester (methyl) acrylic acid in the photosensitive polymer combination of the present invention
Ester (F-1) is used as the general name in main chain with (methyl) acrylate of more than one ester bond, amino
Formic acid esters (methyl) acrylate (F-2) is used as have more than one amino-formate bond in main chain
The general name of (methyl) acrylate, epoxy (methyl) acrylate (F-3) be used as to make 1 official can more than
Epoxide react with (methyl) acrylic acid and obtain the general name of (methyl) acrylate, (gathering)
Ether (methyl) acrylate (F-4) is used as (methyl) acrylic acid in main chain with more than one ehter bond
The general name of ester, (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester (F-5) are used as main chain
For straight chained alkyl, branched alkyl, can be in straight chain or end has halogen atom and/or hydroxyl
The general name of (methyl) acrylate, (methyl) acrylate (F-6) with aromatic rings is used as at main chain
Or side chain has the general name of (methyl) acrylate of aromatic rings, there is (methyl) of alicyclic structure
Acrylate (F-7) is used as to have in main chain or side chain to contain oxygen atom in construction unit
Or the general name of (methyl) acrylate of the alicyclic structure of nitrogen-atoms.
As can (gathering) ester (methyl) third in the photosensitive polymer combination of the present invention
Olefin(e) acid ester (F-1), can enumerate such as: caprolactone modification (methyl) acrylic acid 2-hydroxy methacrylate, ring
Oxidative ethane and/or epoxy pronane modification phthalic acid (methyl) acrylate, ethylene-oxide-modified
The simple functions (gathering) such as succinic acid (methyl) acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate
Ester (methyl) esters of acrylic acid；3-hydroxypivalic acid ester neopentyl glycol two (methyl) acrylate, in oneself
Ester modified 3-hydroxypivalic acid ester neopentyl glycol two (methyl) acrylate, epoxychloropropane modified adjacent benzene
Dioctyl phthalate two (methyl) acrylate；To trimethylolpropane or 1 mole of addition of glycerol 1 mole with
On 6-caprolactone, gamma-butyrolacton, the annular lactone compound such as δ-valerolactone and the trihydroxylic alcohol that obtains
List (methyl) acrylate, two (methyl) acrylate or three (methyl) acrylate；
To tetramethylolmethane or the 6-caprolactone of 1 mole of addition of double trimethylolpropane more than 1 mole,
The annular lactone compound such as gamma-butyrolacton, δ-valerolactone and list (methyl) propylene of tetrahydroxylic alcohol that obtains
Acid esters, two (methyl) acrylate, three (methyl) acrylate or four (methyl) acrylate；Right
6-caprolactone that 1 mole of addition of dipentaerythritol is more than 1 mole, gamma-butyrolacton, δ-valerolactone etc.
Annular lactone compound and list (methyl) acrylate of hexahydroxylic alcohols that obtains or many (methyl) propylene
Acid esters；
As (gathering) ethylene glycol, (gathering) propylene glycol, (gathering) tetramethylene glycol, (gathering) butanediol, 3-
Methyl isophthalic acid, the glycol component such as 5-pentanediol, hexanediol and maleic acid, fumaric acid, succinic acid, oneself
Diacid, phthalic acid, M-phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Polyprotic acid and their acid such as dimeric dibasic acid, decanedioic acid, Azelaic Acid, 5-sodium sulfo isophthalate
(methyl) acrylate of the PEPA of the product of acid anhydride；Comprise above-mentioned glycol component,
Polyprotic acid and the annular lactone of their anhydride and 6-caprolactone, gamma-butyrolacton, δ-valerolactone etc.
(methyl) acrylate of modified poly ester glycol etc. multifunctional (gathering) ester (methyl) esters of acrylic acid etc.,
But it is not limited to these.
Can carbamate (methyl) third in the photosensitive polymer combination of the present invention
Olefin(e) acid ester (F-2) is the hydroxy compounds by having at least one (methyl) acryloxy
(F-2-A) the total of (methyl) acrylate is obtained with the reaction of isocyanate compound (F-2-B)
Claim.
As hydroxy compounds (F-2-A) concrete with at least one (methyl) acryloxy
Example, can enumerate such as: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxyl third
Ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl, hexamethylene diformazan
Alcohol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl)
Acrylate, tetramethylolmethane three (methyl) acrylate, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group
Various (methyl) acrylate compounds with hydroxyl such as propyl ester and the above-mentioned (first with hydroxyl
Base) the ring-opening reaction product etc. of acrylate compounds and 6-caprolactone.
As the concrete example of isocyanate compound (F-2-B), can enumerate such as: different to benzene two
Cyanate, m-benzene diisocyanate, xylol diisocyanate, meta-xylene two Carbimide.
Ester, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 4,4 '-diphenyl methane two are different
The aromatic diisocyanate class such as cyanate, naphthalene diisocyanate；Isophorone diisocyanate,
Hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, hydrogenated xylylen two are different
The aliphatic such as cyanate, norborene diisocyanate, lysinediisocyanate or alicyclic ring knot
The diisocyanates of structure；More than one biuret type of isocyanate-monomer, maybe by upper
The polyisocyanates such as the isocyanates form stating diisocyanate cpd trimerizing and obtain；Logical
The urethane crossing above-mentioned isocyanate compound and above-mentioned polyol compound reacts and obtains
The polyisocyanates etc. arrived.
It should be noted that when obtaining carbamate (methyl) acrylate, there is (first
Base) reaction of hydroxy compounds (F-2-A) and isocyanate compound (F-2-B) of acryloxy
In, it is also possible at random make polyhydric alcohol react.
As the polyhydric alcohol that can use, can enumerate such as: neopentyl glycol, 3-methyl isophthalic acid, 5-
The carbon numbers such as pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-HD are 1～10
The trihydroxylic alcohols such as aklylene glycol, trimethylolpropane, tetramethylolmethane, Tricyclodecane Dimethanol,
Double (methylol) hexamethylene etc. has the alcohol etc. of cyclic skeleton；And by these polyhydric alcohol with polynary
Acid (such as succinic acid, phthalic acid, hexahydrophthalic anhydride, p-phthalic acid, oneself two
Acid, Azelaic Acid, tetrabydrophthalic anhydride etc.) reaction and obtain PEPA, pass through
Caprolactone alcohol, polycarbonate polyol that polyhydric alcohol obtains with the reaction of 6-caprolactone are (the most logical
Cross the PCDL etc. that 1,6-HD obtains with the reaction of diphenyl carbonate) or polyethers many
Unit alcohol (such as Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, ethylene-oxide-modified bis-phenol
A etc.) etc..
Can epoxy (methyl) acrylate in the photosensitive polymer combination of the present invention
(F-3) it is that the epoxy resin making the epoxy radicals more than containing 1 functionality reacts with (methyl) acrylic acid
And obtain the general name of (methyl) acrylate.Ring as the raw material of epoxy (methyl) acrylate
The concrete example of epoxy resins, can enumerate: hydroquinone diglycidyl ether, catechol two contract
The phenyl diglycidyl ethers such as water glycerin ether, resorcinolformaldehyde resin；Bisphenol A-type ring
Double (the 4-hydroxy benzenes of epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2-
Base) the biphenol type epoxy compound such as epoxide of-1,1,1,3,3,3-HFC-236fa；A Hydrogenated Bisphenol A
A type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, A Hydrogenated Bisphenol A S type epoxy resin, hydrogen
The A Hydrogenated Bisphenol A types such as the epoxide of double (4-the hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa of change 2,2-
Epoxide；The halos such as brominated bisphenol-A type epoxy resin, bromobisphenol F type epoxy resin
Biphenol type epoxy compound；The ester ring types two such as cyclohexanedimethanodiglycidyl diglycidyl ether compound contract
Water glycerin ether compound；1,6 hexanediol diglycidylether, 1,4-butanediol diglycidyl ether,
The aliphatic diglycidylether compounds such as diethylene glycol diglycidyl glycerin ether；Polysulfide (Port リ
サ Le Off ァ イ De) the polysulfide type 2-glycidyl ether compound such as diglycidyl ether；Phenolic aldehyde
Type epoxy resin, cresol novolak type epoxy resin, three hydroxyphenyl methane type asphalt mixtures modified by epoxy resin
Fat, dicyclopentadiene phenol type epoxy resin, united phenol-type epoxy resin, bisphenol-A phenolic are clear
Paint shaped epoxy resin, epoxy resin containing naphthalene skeleton, hetero ring type epoxy resin etc..
As can (gathering) ether (methyl) third in the photosensitive polymer combination of the present invention
Olefin(e) acid ester (F-4), can enumerate such as: (methyl) acrylate, butoxy ethyl, butoxy three second two
Alcohol (methyl) acrylate, epoxychloropropane modified (methyl) butyl acrylate, (methyl) acrylic acid
Dihydro dicyclopentadiene epoxide ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, ethyl carbitol
(methyl) acrylate, (methyl) acrylate, Nonylphenoxy Polyethylene Glycol (methyl)
The simple functions such as acrylate (gathering) ether (methyl) esters of acrylic acid；
Polyethylene Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polybutadiene
The aklylene glycols such as alcohol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate
Two (methyl) esters of acrylic acid；By oxirane and the copolymer of expoxy propane, propylene glycol and tetrahydrochysene
The copolymer of furan, poly-isoprene, hydrogenate poly-isoprene, polybutadiene diol, hydrogenation
The polyols such as hydrocarbon polyols class such as polybutadiene diol derive with (methyl) acrylic acid
Multifunctional (methyl) esters of acrylic acid；Epoxy second to 1 mole of addition of neopentyl glycol more than 1 mole
The cyclic ethers such as alkane, expoxy propane, epoxy butane and two (methyl) acrylate of dihydroxylic alcohols of obtaining；
Two (methyl) propylene of the alkylene oxide modifier of the bisphenols such as bisphenol-A, Bisphenol F, bisphenol S
Acid esters；The alkylene oxide of the A Hydrogenated Bisphenol A classes such as hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A S changes
Property thing two (methyl) acrylate；To trimethylolpropane or 1 mole of addition of glycerol more than 1 mole
Oxirane, expoxy propane, the cyclic ether compound such as epoxy butane and the trihydroxylic alcohol that obtains
Single (methyl) acrylate, two (methyl) acrylate or three (methyl) acrylate；
To tetramethylolmethane or the oxirane of 1 mole of addition of double trimethylolpropane more than 1 mole,
The cyclic ether compound such as expoxy propane, epoxy butane and list (methyl) acrylic acid of trihydroxylic alcohol that obtains
Ester, two (methyl) acrylate, three (methyl) acrylate or four (methyl) acrylate；To two
Oxirane that 1 mole of addition of tetramethylolmethane is more than 1 mole, expoxy propane, epoxy butane etc.
3～6 officials of cyclic ether compound and the hexahydroxylic alcohols that obtains can (methyl) acrylate etc. multifunctional (gathering)
Ether (methyl) esters of acrylic acid etc..
As can (methyl) alkyl acrylate in the photosensitive polymer combination of the present invention
Base ester or (methyl) acrylic acid alkylene ester (F-5), can enumerate such as: (methyl) acrylic acid methyl ester.,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl)
Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) propylene
Acid 2-Octyl Nitrite, (methyl) lauryl acrylate, (methyl) 1-Octyl acrylate, (methyl) propylene
Acid different monooctyl ester, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) propylene
Acid stearyl ester, the different stearyl ester of (methyl) acrylic acid, (methyl) isobornyl acrylate, (methyl) third
Olefin(e) acid dihydro dicyclopentadiene base ester, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, (first
Base) acrylic acid dihydro dicyclopentadiene base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid
3-methyl cyclohexanol ester, (methyl) acrylic acid 1-adamantane esters, 2-ethylhexyl carbitol (methyl)
The simple functions such as acrylate (methyl) esters of acrylic acid；
Ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butanediol
Two (methyl) acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl)
Acrylate, 2-methyl isophthalic acid, 8-ethohexadiol two (methyl) acrylate, 1,9-nonanediol two (methyl)
Two (methyl) acrylate of the hydrocarbon glycol such as acrylate, 1,10-decanediol two (methyl) acrylate
Class；
List (methyl) acrylate of trimethylolpropane, two (methyl) acrylate or three (methyl)
Acrylate (following, use " many " as two, three, the polyfunctional general name of the fourth class), glycerol
Single (methyl) acrylate or many (methyl) acrylate, single or multiple (methyl) propylene of tetramethylolmethane
Acid esters, single or multiple (methyl) acrylate of double trimethylolpropane, dipentaerythritol single or multiple
Single or multiple (methyl) third of the polyhydric alcohol such as trihydroxylic alcohol, tetrahydroxylic alcohol, hexahydroxylic alcohols such as (methyl) acrylate
Olefin(e) acid esters；
(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) propylene
(methyl) acrylic compounds containing hydroxyl such as acid 4-hydroxybutyl；Deng.
As having aromatic rings in the photosensitive polymer combination of the present invention
(methyl) acrylate (F-6), can enumerate such as: (methyl) phenyl acrylate, (methyl) propylene
The simple functions such as acid benzyl ester (methyl) esters of acrylic acid；Bisphenol-A two (methyl) acrylate, Bisphenol F
Two (methyl) acrylate etc. two (methyl) esters of acrylic acid etc., but it is not limited to these.
As having alicyclic structure in the photosensitive polymer combination of the present invention
(methyl) acrylate (F-7), can enumerate such as: (methyl) cyclohexyl acrylate, (methyl) third
Olefin(e) acid ring pentyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid dihydro dicyclopentadiene
Base ester etc. has simple function (methyl) esters of acrylic acid of alicyclic structure；Hydrogenated bisphenol A, hydrogenation pair
Two (methyl) acrylate of the A Hydrogenated Bisphenol A classes such as phenol F；Tricyclodecane Dimethanol two (methyl) propylene
Acid esters etc. have multi-functional (methyl) esters of acrylic acid of circulus；(methyl) acrylic acid tetrahydrochysene
Bran ester etc. has ester ring type (methyl) acrylate of oxygen atom etc. in the structure；Deng, but be not limited to
These.
It addition, as having (methyl) in the photosensitive polymer combination of the present invention
The compound of acryloyl group, in addition to above-mentioned compound, it is also possible to use such as: (methyl)
The product of acrylate copolymer and (methyl) glycidyl acrylate or (methyl) acrylic acid
Poly-(methyl) acrylate copolymers such as ethylene oxidic ester polymer and (methyl) acrylic acid product
(methyl) acrylate；(methyl) acrylate etc. has (methyl) third of amino
Olefin(e) acid ester；Isocyanuric acid (methyl) acrylate such as isocyanuric acid three (methyl) acryloyl-oxy ethyl ester；
There is (methyl) acrylate of silicone matrix；Polybutadiene (methyl) acrylate, trimerization
Cyanamide (methyl) acrylate etc..
It addition, as can in the photosensitive polymer combination of the present invention containing Malaysia
The compound (F-8) of imide, can enumerate such as: N-normal-butyl maleimide, N-are own
Base maleimide, ethyl carbonate 2-dimaleoyl imino ethyl ester, propyl carbonate 2-maleimide
The monofunctional aliphatic horses such as aminoethyl, N-ethyl (2-maleimidoethyl) carbamate
Carry out acid imide；The ester ring type simple function maleimides such as N-N-cyclohexylmaleimide；N,N-
Double (the 3-dimaleoyl imino propyl group) ether of hexa-methylene BMI, polypropylene glycol, carbonic acid are double
The aliphatic bismaleimide amines such as (2-maleimidoethyl) ester；1,4-dimaleimide
The ester ring type spans such as butylcyclohexane, isophorone double carbamate double (NEM)
Carry out acid imide；Carry out being esterified by maleimide guanidine-acetic acid and polytetramethylene glycol and obtain
Maleimide compound, the tetraoxane of maleimidocaproic acid with tetramethylolmethane is added
The maleimide compounds becoming thing to carry out being esterified and to obtain etc. are by carboxyl maleimide derivatives
Carry out being esterified with various (polynary) alcohol and obtain (gathering) ester (gathering) maleimide compound etc., but
It is not limited to these.
As can (methyl) acrylamide in the photosensitive polymer combination of the present invention
Compound (F-9), can enumerate such as: acryloyl morpholine, N-isopropyl (methyl) acrylamide etc.
Mono-functional's (methyl) acrylic amide；Di-2-ethylhexylphosphine oxide (methyl) acrylamide etc. multifunctional (methyl)
Acrylic amide etc..
As can unsaturated polyester (UP) in the photosensitive polymer combination of the present invention
(F-10), can enumerate such as: the maleic acid esters such as dimethyl maleate, ethyl maleate.；
The multi-unsaturated carboxylic acid such as maleic acid, fumaric acid and the esterification reaction product of polyhydric alcohol.
Can polymerizable compound (F) in the photosensitive polymer combination of the present invention preferred
And with excellent (methyl) alkyl acrylate of low viscosity and light resistance, workability or (methyl) propylene
Acid alkylene ester (F-5), but it is not limited to above-claimed cpd, if having altogether with above-mentioned (E) composition
The compound of poly-property, then can be without particular limitation and with the compound of one or more.
Wherein, preferably: for (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester etc. and
Have C5～C35, more preferably C15～C35 long-chain there is (methyl) acryloxy
Compound.This is because, by having a structure in which, the compatibility and the transparency can be obtained
Excellent photosensitive polymer combination.
In the photosensitive polymer combination of the present invention, the ratio as above-mentioned (E) and (F) composition does not has
There is restriction especially, relative to (E) composition 100 weight %, preferably comprise 10～2000 weight %
(F) composition, particularly preferably (F) composition containing 20～1000 weight %.
As the Photoepolymerizationinitiater initiater (G) used in the photosensitive polymer combination of the present invention
Concrete example, can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether,
The benzoin classes such as benzoin isobutyl ether；1-Phenylethanone., 2,2-diethoxy-2-phenyl acetophenone, 1,1-
Dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxyl
The 1-Phenylethanone .s such as cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone
Class；The Anthraquinones such as 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone；2,4-
The thioxanthene ketones such as diethyl thioxanthone, ITX, CTX；1-Phenylethanone. diformazan
The ketal classes such as base ketal, benzoin dimethylether；Benzophenone, 4-benzoyl-4 '-methyldiphenyl
The benzophenones such as thioether, 4,4 '-bis-methylamino benzophenone；2,4,6-trimethylbenzoyl
The phosphinoxidess etc. such as diphenyl phosphine oxide, double (2,4,6-trimethylbenzoyl) phenyl phosphine oxide.
As their adding proportion, the solid constituent of photosensitive polymer combination is set to 100 weight %
Time, usually 0.01～30 weight %, preferably 0.1～25 weight %.
They can be used alone or use as mixture of more than two kinds, furthermore, it is possible to
With the tertiary amine such as triethanolamine, methyl diethanolamine, N, N-dimethyl ethyl aminobenzoate, N, N-
The accelerator etc. such as benzoic acid derivative such as dimethylaminobenzoic acid isopentyl ester are applied in combination.As this
The addition of a little accelerator, being added as needed on relative to Photoepolymerizationinitiater initiater (G) is 100 weights
The amount of amount below %.
Additionally, the photosensitive polymer combination of the present invention according to purposes can use aptly non-instead
Answering property compound, inorganic filler, organic filler, silane coupler, viscosifier, froth breaking
Agent, levelling agent, plasticizer, antioxidant, UV absorbent, fire retardant, pigment, dye
Material etc..
As the concrete example of above-mentioned nonreactive compound, for the reactive low or liquid of anergy
State or the oligomer of solid-state or resin, can enumerate: (methyl) alkyl acrylate copolymer, ring
Epoxy resins, liquid polybutadiene, dicyclopentadiene derivant, saturated polyester oligomer, diformazan
Benzene resin, polyether polyols with reduced unsaturation, ketone resin, diallyl phthalate polymer (DAP
Resin), Petropols, rosin resin, fluorine-containing type oligomer, silicon quasi-oligomer, O-phthalic
Esters of gallic acid, phosphoric acid ester, diol-lipid, citric acid ester type, aliphatic dibasic acid ester, fat
Fat esters of gallic acid, epoxy plasticiser, Semen Ricini oils, terpenes hydrogenated resin, there is poly-isoamyl
Diene skeleton, polybutadiene skeleton or the oligomer of dimethylbenzene skeleton or polymer and carboxylate thereof,
Dienite, epoxide modified polybutadiene, butadiene-styrene random copolymer, poly-fourth
The softening agents etc. such as alkene, but it is not limited to these.This composition is in ultraviolet-curing resin composition
Part by weight be usually 10～80 weight %, be preferably 10～70 weight %.
As above-mentioned inorganic filler, can enumerate such as: silicon dioxide, silicon oxide, carbonic acid
Calcium, calcium silicates, magnesium carbonate, magnesium oxide, Talcum, Kaolin, calcined clay, zinc oxide,
Zinc sulfate, aluminium hydroxide, aluminium oxide, glass, Muscovitum, barium sulfate, alumina white, zeolite,
Hollow silica microballon (silica ballon), glass hollow microballon (glass ballon) etc..These
Can also be by adding silane coupler, titante coupling agent, aluminum class occasionally in inorganic filler
Connection agent, zirconate coupling agent etc. and be allowed to the methods such as reaction and have halogen radical, epoxy radicals,
The functional group such as hydroxyl, sulfydryl.
As above-mentioned organic filler, can enumerate such as: benzoguanamine resin, polysiloxanes
Resin, Low Density Polyethylene, high density polyethylene (HDPE), vistanex, ethylene-acrylic acid copolymer
Thing, polystyrene, acrylic copolymer, plexiglass, fluorine resin,
Nylon 12, nylon 6/66, phenolic resin, epoxy resin, polyurethane resin, polyimides tree
Fat etc..
As silane coupler, can enumerate such as: γ-glycydoxy trimethoxy
Silane coupler, four (the 2,2-diallyl epoxides such as base silane or γ-r-chloropropyl trimethoxyl silane
Methyl isophthalic acid-butyl) double (double tridecyl) phosphite ester titanate esters, double (dioctyl pyrophosphate base) ethylene
The titante coupling agents such as titanate esters；The aluminum class coupling agents such as acetyl alkoxyl aluminum-diisopropoxide；Second
The zirconium class coupling agents such as acyl acetone-zirconium complex；Deng.
The viscosifier that can use in the photosensitive polymer combination of the present invention, defoamer, stream
If flat agent, plasticizer, antioxidant, UV absorbent, fire retardant, pigment and dyestuff
It is known usual material, then can not have in the range of its curable, resin properties not damaging
Have and use to restriction especially.
In order to obtain the photosensitive polymer combination of the present invention, above-mentioned each composition is mixed,
The order of mixing, method are not particularly limited.
Various additives in the composition in the presence of, various additives are saturating at light-cured type
Part by weight in gelatin adhesive composition is 0.01～3 weight %, is preferably 0.01～1 weight
Amount %, more preferably 0.02～0.5 weight %.
The photosensitive polymer combination of the present invention substantially need not solvent but it also may utilizes example
As the acetate esters such as the ketone such as butanone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate,
The aromatic hydrocarbons such as benzene,toluene,xylene etc. and other the most conventional organic solvent are by this
Use after bright photosensitive polymer combination dilution.
The photosensitive polymer combination of the present invention can be by the wavelength of irradiation 180～500nm
Ultraviolet or visible ray are polymerized.Alternatively, it is also possible to penetrated by the energy beyond ultraviolet
The irradiation of line or utilize heat to make it solidify.
As ultraviolet or the luminous source of visible ray of wavelength 180～500nm, example can be enumerated
Such as: low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, chemical lamp, black
Light modulation, mercury xenon lamp, Excimer lamp, short-arc lamp, helium cadmium laser, argon laser, excimer laser,
Sunlight.
The flexibility excellence of the photosensitive polymer combination of the present invention and weatherability, light resistance height,
And in addition to needing to keep transparent optical applications, also at ink, plastic paint, paper
Printing, metal coated, various coating applications, lining, adhesive and the electricity such as application of furniture
Insulating varnish, insulating trip, plywood, printed base plate, resist ink in sub-field, partly lead
In multiple fields such as body sealant useful.As more specifically purposes, at plano-convex printing ink, soft
The ink areas such as printing ink, gravure ink, ink for screen printing, light Herba Euphorbiae Helioscopiae field, paper smears neck
Territory, carpenter are coated with paint field, beverage can smears or printing-ink field, flexible packaging film
Cloth agent, printing-ink or binding agent, heat-sensitive paper, thermosensitive film smears, printing-ink, glue
Stick, binding agent or coating optical fibers agent, liquid crystal indicator, organic EL display, touch-control
The air gap filler of the display devices such as panel type image display device is (between display device and surface plate
The filler in gap) etc. useful in purposes.
Embodiment
Hereinafter, by embodiment, the present invention is carried out more specific description, but the invention is not restricted to
Following embodiment.
Synthesis example 1
In there is reflux condenser, blender, thermometer, thermostatic reactor,
Add Tso Tat Co., Ltd., Japan manufacture GI-2000 (iodine number: 12.2, hydroxyl value:
46.8mgKOH/g) 523.93g (0.22mol) is as hydrogenated butadiene polymer polyol compound, day oil
The PEG#400 (hydroxyl value: 278mgKOH/g) 4.64g (0.012mol) that Co., Ltd. manufactures is as poly-
S-1800A (the different stearyl ester of the acrylic acid) 200.31g that ethylene glycol, KCC of Xin Zhong village manufacture
As polymerizable compound, 4-methoxyphenol 0.36g as polymerization inhibitor, and stir until uniformly,
Internal temperature is set as 50 DEG C.It follows that interpolation isophorone diisocyanate
61.35g (0.28mol) is as polyisocyanate compound, and reacts until reaching at 80 DEG C
NCO content to target.It follows that add what Osaka Organic Chemical Industry Co., Ltd. manufactured
2-Hydroxy ethyl acrylate 11.00g (0.095mol) is as (methyl) third with more than 1 hydroxyl
Enoic acid ester compounds, tin octoate 0.18g are as urethane catalysts, and at 80 DEG C
Under react, as the terminal of reaction when NCO content is reached less than 0.1%, thus obtain
Urethanes (E-1).
Synthesis example 2
In there is reflux condenser, blender, thermometer, thermostatic reactor,
Add Tso Tat Co., Ltd., Japan manufacture GI-2000 (iodine number: 12.2, hydroxyl value:
46.8mgKOH/g) 431.62g (0.18mol) is as hydrogenated butadiene polymer polyol compound, day oil
The PEG#400 (hydroxyl value: 278mgKOH/g) 8.07g (0.020mol) that Co., Ltd. manufactures is as poly-
S-1800A (the different stearyl ester of the acrylic acid) 167.54g that ethylene glycol, KCC of Xin Zhong village manufacture
As polymerizable compound, 4-methoxyphenol 0.30g as polymerization inhibitor, and stir until uniformly,
Internal temperature is set as 50 DEG C.It follows that interpolation isophorone diisocyanate
53.35g (0.24mol) is as polyisocyanate compound, and reacts until reaching mesh at 80 DEG C
Target NCO content.It follows that add the propylene that Osaka Organic Chemical Industry Co., Ltd. manufactures
Acid-2-hydroxy methacrylate 9.57g (0.082mol) is as (methyl) acrylic acid with more than 1 hydroxyl
Ester compounds, tin octoate 0.15g are as urethane catalysts, and at 80 DEG C
React, as the terminal of reaction when NCO content is reached less than 0.1%, resulting in
Urethanes (E-2).
Synthesis example 3
In there is reflux condenser, blender, thermometer, thermostatic reactor,
Add Tso Tat Co., Ltd., Japan manufacture GI-2000 (iodine number: 12.2, hydroxyl value:
46.8mgKOH/g) 441.21g (0.18mol) is as hydrogenated butadiene polymer polyol compound, day oil
The PEG#2000 (hydroxyl value: 51.6mgKOH/g) 100.04g (0.046mol) that Co., Ltd. manufactures makees
S-1800A (the different tristearin of acrylic acid manufactured for Polyethylene Glycol, KCC of Xin Zhong village
Ester) 204.54g as polymerizable compound, 4-methoxyphenol 0.37g is as polymerization inhibitor, and stir
Mix until uniformly, internal temperature being set as 50 DEG C.It follows that add isophorone two isocyanide
Acid esters 61.35g (0.28mol) is as polyisocyanate compound, and reacts until reaching at 80 DEG C
NCO content to target.It follows that add what Osaka Organic Chemical Industry Co., Ltd. manufactured
2-Hydroxy ethyl acrylate 11.00g (0.095mol) is as (methyl) third with more than 1 hydroxyl
Enoic acid ester compounds, tin octoate 0.18g are as urethane catalysts, and at 80 DEG C
Under react, as the terminal of reaction when NCO content is reached less than 0.1%, thus obtain
Urethanes (E-3).
Synthesis example 4
In there is reflux condenser, blender, thermometer, thermostatic reactor,
Add Cray Willie manufacture KRASOL HLBH-P2000 (iodine number: 13.5, hydroxyl value:
0.89meq/g) 404.49g (0.18mol) is as hydrogenated butadiene polymer polyol compound, day oil strain formula
The PEG#200 (hydroxyl value: 518mgKOH/g) 39.00g (0.18mol) that commercial firm manufactures is as poly-second two
S-1800A (the different stearyl ester of the acrylic acid) 202.20g that alcohol, KCC of Xin Zhong village manufacture makees
For polymerizable compound, 4-methoxyphenol 0.36g as polymerization inhibitor, and stir until uniformly,
Internal temperature is set as 50 DEG C.It follows that interpolation isophorone diisocyanate
120.04g (0.54mol) is as polyisocyanate compound, and reacts until reaching mesh at 80 DEG C
Target NCO content.It follows that add the propylene that Osaka Organic Chemical Industry Co., Ltd. manufactures
Acid-2-hydroxy methacrylate 43.06g (0.37mol) is as (methyl) acrylic acid with more than 1 hydroxyl
Ester compounds, tin octoate 0.18g are as urethane catalysts, and at 80 DEG C
React, as the terminal of reaction when NCO content is reached less than 0.1%, resulting in
Urethanes (E-4).
Coordinating example 1
By urethanes (E-1) 20 mass parts of synthesis example 1, KCC of Xin Zhong village
S-1800A (the different stearyl ester of acrylic acid) 19 mass parts, the Japan Oil Co that manufacture manufacture
BLEMMER LA (lauryl acrylate) 10 mass parts, An Yuan KCC manufacture
CLEARON M-105 (aromatic modified hydrogenated terpene resin) 18 mass parts, JX day ore deposit day stone energy
LV-100 (polybutene) 10 mass parts, Tso Tat Co., Ltd., Japan that source Co., Ltd. manufactures manufacture
GI-2000 (1,2-hydrogenated polybutadiene diol) 20 mass parts, Osaka Organic Chemical Industry strain formula
4-HBA (acrylic acid 4-hydroxybutyl) 3 mass parts, LAMBSO company that commercial firm manufactures manufacture
Speedcure TPO (2,4,6-trimethyl benzoyl diphenyl base phosphine oxide) 0.5 mass parts, bar
IRGACURE 184 (1-hydroxycyclohexylphenylketone) the 0.5 mass parts heating that Si Fu company manufactures
To 70 DEG C and mix, resulting in the resin combination of the present invention.This resin combination
Viscosity be 4200mPa s.
Coordinating example 2
By urethanes (E-2) 20 mass parts of synthesis example 2, KCC of Xin Zhong village
S-1800A (the different stearyl ester of acrylic acid) 19 mass parts, the Japan Oil Co that manufacture manufacture
BLEMMER LA (lauryl acrylate) 10 mass parts, An Yuan KCC manufacture
CLEARON M-105 (aromatic modified hydrogenated terpene resin) 18 mass parts, JX day ore deposit day stone energy
LV-100 (polybutene) 10 mass parts, Tso Tat Co., Ltd., Japan that source Co., Ltd. manufactures manufacture
GI-2000 (1,2-hydrogenated polybutadiene diol) 20 mass parts, Osaka Organic Chemical Industry strain formula
4-HBA (acrylic acid 4-hydroxybutyl) 3 mass parts, LAMBSO company that commercial firm manufactures manufacture
Speedcure TPO (2,4,6-trimethyl benzoyl diphenyl base phosphine oxide) 0.5 mass parts, bar
IRGACURE 184 (1-hydroxycyclohexylphenylketone) the 0.5 mass parts heating that Si Fu company manufactures
To 70 DEG C and mix, resulting in the resin combination of the present invention.This resin combination
Viscosity be 3800mPa s.
Coordinating example 3
By urethanes (E-3) 20 mass parts of synthesis example 3, KCC of Xin Zhong village
S-1800A (the different stearyl ester of acrylic acid) 19 mass parts, the Japan Oil Co that manufacture manufacture
BLEMMER LA (lauryl acrylate) 10 mass parts, An Yuan KCC manufacture
CLEARON M-105 (aromatic modified hydrogenated terpene resin) 18 mass parts, JX day ore deposit day stone energy
LV-100 (polybutene) 10 mass parts, Tso Tat Co., Ltd., Japan that source Co., Ltd. manufactures manufacture
GI-2000 (1,2-hydrogenated polybutadiene diol) 20 mass parts, Osaka Organic Chemical Industry strain formula
4-HBA (acrylic acid 4-hydroxybutyl) 3 mass parts, LAMBSO company that commercial firm manufactures manufacture
Speedcure TPO (2,4,6-trimethyl benzoyl diphenyl base phosphine oxide) 0.5 mass parts, bar
IRGACURE 184 (1-hydroxycyclohexylphenylketone) the 0.5 mass parts heating that Si Fu company manufactures
To 70 DEG C and mix, resulting in the resin combination of the present invention.This resin combination
Viscosity be 4300mPa s.
Coordinating example 4
By urethanes (E-4) 20 mass parts of synthesis example 4, KCC of Xin Zhong village
S-1800A (the different stearyl ester of acrylic acid) 19 mass parts of manufacture, Japan Oil Co's system
BLEMMER LA (lauryl acrylate) 10 mass parts, An Yuan KCC manufacture
CLEARON M-105 (aromatic modified hydrogenated terpene resin) 18 mass parts, JX day ore deposit day stone energy
LV-100 (polybutene) 10 mass parts, Tso Tat Co., Ltd., Japan that source Co., Ltd. manufactures manufacture
GI-2000 (1,2-hydrogenated polybutadiene diol) 20 mass parts, Osaka Organic Chemical Industry strain formula
4-HBA (acrylic acid 4-hydroxybutyl) 3 mass parts, LAMBSO company that commercial firm manufactures manufacture
Speedcure TPO (2,4,6-trimethyl benzoyl diphenyl base phosphine oxide) 0.5 mass parts, bar
IRGACURE 184 (1-hydroxycyclohexylphenylketone) the 0.5 mass parts heating that Si Fu company manufactures
To 70 DEG C and mix, resulting in the resin combination of the present invention.This resin combination
Viscosity be 3000mPa s.
Coordinating example 1～4 is shown in Table 1, and has carried out following evaluation.
Table 1
(viscosity) uses E type viscometer (TV-200: Toki Sangyo Co., Ltd.'s system) to enter at 25 DEG C
Go mensuration.
(refractive index) determines resin with Abbe refractomecer (DR-M2: Atagi Corp.'s system)
Refractive index (25 DEG C).
(cure shrinkage) prepares to be coated with the microscope slide two of the thickness 1mm of fluorine-containing type releasing agent
Sheet, the most a piece of ultraviolet curing resin combination obtained by the coating of releasing agent coated face
Thing makes thickness be 200 μm.Afterwards, by two panels microscope slide with respective releasing agent coated face phase
Mode faced by Hu is fitted.Across glass with high voltage mercury lamp (80W/cm, ozone free) to this
Resin combination irradiates accumulative light quantity 3000mJ/cm2Ultraviolet so that this resin combination
Solidification.Afterwards, peel off two panels microscope slide, thus made the solidfied material of film gravity test.
According to JIS K 7112B method, determine the proportion (DS) of solidfied material.It addition, determine at 25 DEG C
The liquid specific gravity (DL) of resin combination.According to the measurement result of DS and DL, following formula calculate
Cure shrinkage, result is less than 2.5%.
Cure shrinkage (%)=(DS-DL) ÷ DS × 100
(rigidity modulus) prepares the PET film two panels after the demoulding processes, the most a piece of stripping surface
Ultraviolet-curing resin composition obtained by upper coating makes thickness be 200 μm.Afterwards,
Two panels PET film is fitted in the opposed facing mode of respective stripping surface.Across PET film
By high voltage mercury lamp (80W/cm, ozone free) light quantity accumulative to the irradiation of this resin combination
3000mJ/cm2Ultraviolet so that this resin composition.Afterwards, by two panels PET
Film is peeled off, thus has made the solidfied material that rigidity modulus measures.Rigidity modulus ARES (TA
Instruments company system) it is measured.
(absorbance) prepares the microscope slide two panels of thickness 1mm, obtained by the most a piece of upper coating
Ultraviolet-curing resin composition make solidification after thickness be 200 μm.Afterwards, by two
Sheet microscope slide is fitted.Accumulative light quantity is irradiated across glass high voltage mercury lamp (80W/cm, ozone free)
3000mJ/cm2Ultraviolet so that this resin composition, thus made absorbance
The solidfied material measured.For the transparency of obtained solidfied material, use spectrophotometer
(U-3310, new and high technology Co., Ltd. of Hitachi) determines 400～800nm and 400～450nm
Wavelength region in absorbance.As a result of which it is, the absorbance of 400～800nm is more than 90%,
And the absorbance of 400～450nm is more than 90%.
(heat-resisting, moisture-proof adhesivity) prepares microscope slide and the glass of thickness 1mm of thickness 1mm
Glass plate or post the glass plate of thickness 1mm of polarizing coating at one side, in one obtained by coating
Ultraviolet-curing resin composition make thickness be 200 μm, then fit at its coated face
Another one.Across glass high voltage mercury lamp (80W/cm, ozone free), this resin combination is irradiated
Accumulative light quantity 3000mJ/cm2Ultraviolet so that this resin composition, thus make
Adhesivity sample for evaluation.Use this sample, carry out the heat resistant test of 85 DEG C, 60 DEG C of 90%RH
Humidity test, and place 100 hours.In this sample for evaluation, with visually solid to resin
Compound stripping from glass or polarizing coating is confirmed, the most peeling-off.
The present invention is described in detail with reference to specific mode, but, in the essence without departing from the present invention
Can make various changes and modifications in the case of god and scope, this is for those skilled in the art
For be apparent from.
It should be noted that the application is based on the Japan Patent Shen proposed on March 3rd, 2014
Please (2014-40089), it is incorporated herein entirely through the mode quoted.It addition, drawn herein
Institute be incorporated herein with reference to expansion body.
Industrial applicability
The photosensitive polymer combination of the urethanes containing the present invention is excellent due to flexibility
And weatherability, light resistance are high, the transparency is excellent, therefore useful as optical applications component.This
Outward, the solidfied material of the photosensitive polymer combination of the present invention is as laminating Transparence Display structure base board
Adhesive is useful.
Claims (10)
1. a urethanes (E), it is by making following shown compound (A), chemical combination
Thing (B), compound (C) and compound (D) react and obtain,
Compound (A): hydrogenated butadiene polymer polyol compound
Compound (B): Polyethylene Glycol
Compound (C): polyisocyanate compound
Compound (D): there is (methyl) acrylate compounds of more than 1 hydroxyl.
2. urethanes (E) as claimed in claim 1, wherein, hydrogenated butadiene polymer is many
The iodine number of unit's alcoholic compound (A) is less than 20.
3. urethanes (E) as claimed in claim 1 or 2, wherein, Polyethylene Glycol (B)
Number-average molecular weight be 100～4,000.
4. the urethanes (E) as according to any one of claims 1 to 3, wherein, many
Isocyanate compound (C) is aliphatic category diisocyanate cpd.
5. the urethanes (E) as according to any one of Claims 1 to 4, wherein, tool
(methyl) acrylate compounds (D) having more than 1 hydroxyl is (methyl) acrylic acid 2-hydroxyl second
Ester.
6. a photosensitive polymer combination, it contains according to any one of Claims 1 to 5
Urethanes (E) and polymerizable compound (F) in addition to (E).
7. photosensitive polymer combination as claimed in claim 6, wherein, polymerizable compound
(F) it is (methyl) alkyl acrylate or (methyl) acrylic acid alkylene ester.
Photosensitive polymer combination the most as claimed in claims 6 or 7, it contains photopolymerization and draws
Send out agent (G).
9. a solidfied material, its photoresist according to any one of claim 6～8
The solidfied material of compositions.
10. a manufacture method for the photosensitive polymer combination described in claim 6 or 7,
It is characterized in that, synthesis of polyurethane compound (E) in the presence of polymerizable compound (F).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-040089 | 2014-03-03 | ||
| JP2014040089A JP6172753B2 (en) | 2014-03-03 | 2014-03-03 | Polyurethane compound and resin composition containing the same |
| PCT/JP2015/056033 WO2015133416A1 (en) | 2014-03-03 | 2015-03-02 | Polyurethane compound and resin composition containing same, cured product of said resin composition, and method for producing said resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105916907A true CN105916907A (en) | 2016-08-31 |
Family
ID=54055222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580004580.4A Pending CN105916907A (en) | 2014-03-03 | 2015-03-02 | Polyurethane compound and resin composition containing same, cured product of said resin composition, and method for producing said resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6172753B2 (en) |
| KR (1) | KR20160128991A (en) |
| CN (1) | CN105916907A (en) |
| TW (1) | TWI635107B (en) |
| WO (1) | WO2015133416A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852265A (en) * | 2018-12-28 | 2019-06-07 | 新纶复合材料科技（常州）有限公司 | A kind of aluminum plastic film outer layer polyurethane glue, aluminum plastic film and preparation method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6320255B2 (en) * | 2014-09-12 | 2018-05-09 | 日本化薬株式会社 | Resin composition |
| JP6643846B2 (en) * | 2015-09-18 | 2020-02-12 | 日本化薬株式会社 | Polyurethane compound and resin composition containing the same |
| JP2017057349A (en) * | 2015-09-18 | 2017-03-23 | 日本化薬株式会社 | Polyurethane compound and resin composition containing the same |
| TW201731989A (en) * | 2015-12-22 | 2017-09-16 | 日本合成化學工業股份有限公司 | Active energy ray-curable resin composition and method for producing same |
| CN106366729A (en) * | 2016-08-30 | 2017-02-01 | 安徽翰文运动用品股份有限公司 | Oil paint applying to surface of badminton racket and construction method thereof |
| JP7208067B2 (en) * | 2018-03-30 | 2023-01-18 | 株式会社コーセー | Water-in-oil make-up cosmetic |
| JP2020084039A (en) * | 2018-11-26 | 2020-06-04 | 三菱ケミカル株式会社 | Urethan (meth)acrylate |
| CN113853395B (en) * | 2019-05-24 | 2024-05-03 | 佳能株式会社 | Curable resin composition and cured product thereof |
| JP7489911B2 (en) | 2020-12-11 | 2024-05-24 | 日本化薬株式会社 | Liquid crystal sealant for liquid crystal dripping method |
| JP7432492B2 (en) | 2020-12-11 | 2024-02-16 | 日本化薬株式会社 | Liquid crystal sealant for liquid crystal dripping method |
| JP2023003576A (en) * | 2021-06-24 | 2023-01-17 | Dic株式会社 | Resin, curable resin composition, cured product, insulating material and resist member |
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- 2015-03-02 WO PCT/JP2015/056033 patent/WO2015133416A1/en active Application Filing
- 2015-03-02 CN CN201580004580.4A patent/CN105916907A/en active Pending
- 2015-03-03 TW TW104106619A patent/TWI635107B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201602149A (en) | 2016-01-16 |
| KR20160128991A (en) | 2016-11-08 |
| TWI635107B (en) | 2018-09-11 |
| JP6172753B2 (en) | 2017-08-02 |
| JP2015164981A (en) | 2015-09-17 |
| WO2015133416A1 (en) | 2015-09-11 |
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Application publication date: 20160831 |