CN108727556A - Carbamate（Methyl）Acrylate, activity energy-line solidifying type resin composition, solidfied material and film - Google Patents
Carbamate（Methyl）Acrylate, activity energy-line solidifying type resin composition, solidfied material and film Download PDFInfo
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- CN108727556A CN108727556A CN201810330326.9A CN201810330326A CN108727556A CN 108727556 A CN108727556 A CN 108727556A CN 201810330326 A CN201810330326 A CN 201810330326A CN 108727556 A CN108727556 A CN 108727556A
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- methyl
- acrylate
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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
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- 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
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Abstract
[technical problem] the present invention provides carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied material and films.[technological means] the present invention provides carbamate (methyl) acrylate, carbamate (methyl) acrylate is the reaction product of the compound group containing following compositions：Polyisocyanates (A) without aromatic group, it is addition forms that the polyisocyanates (A) without aromatic group, which has selected from least one of the group being made of isocyanurate group, biuret groups and allophanate group group and/or the polyisocyanates (A) without aromatic group,；And more (methyl) acrylate (B) of polypentaerythritol, more (methyl) acrylate (B) of polypentaerythritol have the polypentaerythritol skeleton of tripolymer or more and contain hydroxyl.
Description
Technical field
The present invention relates to carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied materials
And film.
Background technology
In the past, it is by being bonded tri acetyl cellulose membrane (TAC on polaroid two sides for the polarizer of liquid crystal display device
Film) it is manufactured as protective film, the polaroid is adsorbed with iodine on polyvinyl alcohol film and is oriented by drawing-off etc..Together
When, it is coated with transparent activity energy-line solidifying type resin composition on TAC film surface, is allowed to be formed by curing the overlay film of high rigidity
(hard conating) is protected from damage etc..It has been known that there is contain multifunctional amino first for above-mentioned activity energy-line solidifying type resin composition
The activity energy-line solidifying type resin composition (patent document 1) of acid esters (methyl) acrylate etc..
Existing technical literature
Patent document
[patent document 1] Japanese Unexamined Patent Publication 2009-286924 bulletins
Invention content
Technical problems to be solved by the inivention
Slimming with the liquid-crystal apparatus in recent years centered on handset use and high-quality, said protection film is to film
Change development.Attempt to be allowed to be formed by curing being coated with activity energy-line solidifying type resin composition on such filming protective film
In the case of the hard conating of high rigidity, when solidification the contraction of coating layer cause film to crimp strongly, become and processed in subsequent handling
Property reduce and the reason of panel deformation.On the other hand, the combination for reducing reflecting point (anti-ying point) is being used in order to reduce curling
In the case of object, case hardness is caused to reduce.
Technical problem to be solved by the invention is to provide the surface of basement membrane formed have both high rigidity, low crimpiness,
High marresistance, high-light-fastness cured film optics activity energy-line solidifying type resin composition.
Solve the technological means of technical problem
Present inventor concentrates on studies to solve aforementioned technical problem, finds by using the reaction with specific structure
Product can solve aforementioned technical problem, so as to complete the present invention.
Following items are provided through the invention.
(project 1)
Carbamate (methyl) acrylate, carbamate (methyl) acrylate is containing following compositions
The reaction product of compound group：
Polyisocyanates (A) without aromatic group, the polyisocyanates (A) without aromatic group have choosing
From at least one of the group being made of isocyanurate group, biuret groups and allophanate group group and/or it is described not
Polyisocyanates (A) containing aromatic group is addition forms (ア ダ Network ト body)；And
More (methyl) acrylate (B) of polypentaerythritol, more (methyl) acrylate (B) of polypentaerythritol have three
More than aggressiveness polypentaerythritol skeleton simultaneously contains hydroxyl.
(project 2)
Active energy ray-curable resin group containing carbamate (methyl) acrylate as described in above-mentioned project
Close object.
(project 3)
Activity energy-line solidifying type resin composition as described in above-mentioned project, the active energy ray-curable resin group
It closes object and contains Photoepolymerizationinitiater initiater.
(project 4)
The solidfied material of activity energy-line solidifying type resin composition as described in any one of above-mentioned project.
(project 5)
Film containing the solidfied material as described in above-mentioned project.
In the present invention, it for said one or multiple features, other than the combination expressed, can also provide further
Combination.
Advantageous effect
By using carbamate provided by the present invention (methyl) acrylate, can be formed on the surface of basement membrane simultaneous
Has the cured film of high rigidity, low crimpiness, high marresistance, high-light-fastness.It can be adapted for as a result, it is possible to manufacture
The thin protective film of film substrate.
Specific implementation mode
Among full text of the present invention, the ranges of the numerical value such as value and content of each physical property can suitably set (such as from
It is selected in the value of upper and lower bound recorded in following projects).Specifically, for numerical value α, numerical value α the upper limit for example
Be A1, A2, A3 etc., numerical value α lower limit be, for example, B1, B2, B3 etc. in the case of, the range of numerical value α be, for example, A1 or less, A2 with
Under, A3 or less, B1 or more, B2 or more, B3 or more, A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3~
B1, A3~B2, A3~B3 etc..
[carbamate (methyl) acrylate]
The present invention provides carbamate (methyl) acrylate, carbamate (methyl) acrylate is to contain
There is the reaction product of the compound group of following compositions：
Polyisocyanates (A) without aromatic group, the polyisocyanates (A) without aromatic group have choosing
From at least one of the group being made of isocyanurate group, biuret groups and allophanate group group and/or it is described not
Polyisocyanates (A) containing aromatic group is addition forms；And
More (methyl) acrylate (B) of polypentaerythritol, more (methyl) acrylate (B) of polypentaerythritol have three
More than aggressiveness polypentaerythritol skeleton simultaneously contains hydroxyl.
In the present invention, " (methyl) acrylate " refers to " selected from being made of acrylate and methacrylate
At least one of group ".Similarly, " (methyl) acrylic acid " refers to " selected from the group being made of acrylic acid and methacrylic acid
At least one of ".
In the present invention, " polyisocyanates " refers to the compound with more than two isocyanate group (- N=C=O).
Polyisocyanates (A) can be used alone, and can also use two or more merging.
<Polyisocyanates (A) without aromatic group：Also referred to as (A) ingredient；The polyisocyanate without aromatic group
Cyanate (A) has selected from least one of the group being made of isocyanurate group, biuret groups and allophanate group
Group and/or the polyisocyanates (A) without aromatic group are addition forms>
(have selected from least one of the group being made of isocyanurate group, biuret groups and allophanate group
The polyisocyanates without aromatic group of group)
With selected from least one of the group being made of isocyanurate group, biuret groups and allophanate group base
Group the polyisocyanates without aromatic group be, for example,：Straight-chain aliphatic polyisocyanates, branched aliphatic polyisocyanic acid
The polymer etc. of ester and/or alicyclic polyisocyanates.
Straight-chain aliphatic is, for example, straight-chain alkyl-sub etc..Straight-chain alkyl-sub can be by general formula-(CH2)n(n be 1 or more it is whole
Number) it indicates, e.g.：Methylene, ethylidene, propylidene, positive butylidene, positive pentylidene, positive hexylidene, positive heptamethylene, positive Asia
Octyl, positive nonylene, positive decamethylene (n- デ カ メ チ レ Application base) etc..
Straight-chain aliphatic polyisocyanates is, for example,：Methylene diisocyanate, dimethylene diisocyanate, three methylenes
Group diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, seven methylenes
Group diisocyanate, eight methylene diisocyanates, nine methylene diisocyanates, decamethylene diisocyanate etc..
Branched aliphatic is, for example, branched alkylidene etc..Branched alkylidene is at least one hydrogen of straight-chain alkyl-sub by alkyl
Substituted group, specific example are, for example,：Diethyl pentylidene, trimethyl butylidene, trimethyl pentylidene, trimethyl hexamethylene
(tri-methyl hexamethylene) etc..
Branched aliphatic polyisocyanates is, for example,：Diethyl pentamethylene diisocyanate, two isocyanide of trimethyl butylidene
Acid esters, trimethyl pentamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc..
Alicyclic is, for example, ring alkylidene etc..Ring alkylidene is, for example,：Monocycle ring alkylidene, bridged ring ring alkylidene, condensed ring
Ring alkylidene etc..Meanwhile ring alkylidene can also be that more than one hydrogen is replaced by linear or branched alkyl group.
In the present invention, monocycle refers to the cyclic structure for not having bridged linkage by the inside that carbon covalent bond is formed.Meanwhile
Condensed ring refers to that there are two the ring-types of atom (that is, only there are one be shared (condensation) each other on the side of each ring) altogether for more than two monocycles
Structure.Bridged ring refers to the cyclic structure that more than two monocycles share 3 or more atoms.
Monocycle ring alkylidene is, for example,：Ring pentylidene, cyclohexylene, ring heptamethylene, ring decylene, 3,5,5- front three basic rings
Hexylidene etc..
Bridged ring ring alkylidene is, for example,：Tricyclic decylene, sub- adamantyl (ア ダ マ Application チ レ Application base), sub- norborny
(ノ Le ボ Le ニ レ Application base) etc..
Condensed ring ring alkylidene is, for example, bicyclic decylene etc..
Alicyclic polyisocyanates are, for example,：Single ring alicyclic polyisocyanates, bridged ring alicyclic polyisocyanates, condensed ring
Alicyclic polyisocyanates etc..
Single ring alicyclic polyisocyanates is, for example,：Hydrogenated xylene diisocyanate, isophorone diisocyanate, ring
Pentamethylene diisocyanate, cyclohexylene diisocyanate, ring heptamethylene diisocyanate, ring decylene diisocyanate, 3,
5,5- trimethyl cyclohexylenes diisocyanate, dicyclohexyl methyl hydride diisocyanate etc..
Bridged ring alicyclic polyisocyanates are, for example,：Tricyclic decylene diisocyanate, adamantyl diisocyanate, drop
Bornylene diisocyanate etc..
Condensed ring alicyclic polyisocyanates are, for example, bicyclic decylene diisocyanate etc..
The carbon number of alkylidene is not particularly limited, the upper limit is, for example, 30,29,25,20,15,12,10,9,8,7,6,5,
4,3,2 etc., lower limit is, for example, 29,25,20,15,12,10,9,8,7,6,5,4,3,2,1 etc..In one embodiment, alkylene
The carbon number of base is preferably 1~30, more preferably 1~20, further preferably 1~16, particularly preferably 1~12.
The isocyanuric acid ester-formin of polyisocyanates is indicated by following structural formula (A-1)：
[changing 1]
In formula, R1A~R1EIt is each independently alkyl；R1D~R1EGroup can be different for each structural unit；n1
It is 0 or more integer, n1 is preferably 0~3.
The isocyanuric acid ester-formin of polyisocyanates is, for example,：Duranate(デュラネート)TPA-100,
Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B are (above for Japanese Asahi Chemical Industry (Co., Ltd.)
Manufacture), Coronate (U ロ ネ ー ト) HXR (the isocyanuric acid ester-formin of hexamethylene diisocyanate) (above be this East of day
ソ ー (Co., Ltd.) manufacture), Takenate (タ ケ ネ ー ト) D-127N (isocyanuric acids of hydrogenated xylene diisocyanate
Ester-formin) (being above Mitsui chemical (Co., Ltd.) manufacture), VESTANAT T1890/100 (isophorone diisocyanates
Isocyanuric acid ester-formin (being above エ ボ ニ ッ Network Japanese (Co., Ltd.) manufacture) of ester etc..
The biuret type of polyisocyanates is indicated by following structural formula (A-2)：
[changing 2]
In formula, R2A~R2EIt is each independently alkyl；R2D~R2EGroup can be different for each structural unit；n2
It is 0 or more integer, n2 is preferably 0~3.
The biuret type of polyisocyanates is, for example,：Duranate 24A-100,Duranate 22A-75P,
Duranate 21S-75E (above to be manufactured for Japanese Asahi Chemical Industry (Co., Ltd.)), Desmodur (デ ス モ ジ ュ ー Le)
N3200A (biuret type of hexamethylene diisocyanate) (is SUMITOMO CHEMICAL バ イ エ Le ウ レ タ Application (strain formula meetings above
Society) manufacture) etc..
The allophanic acid ester-formin of polyisocyanates is indicated by following structural formula (A-3)：
[changing 3]
In formula, R3A~R3GIt is each independently alkyl；R3B~R3EGroup can be different for each structural unit；n3
It is 0 or more integer, n3 is preferably 0~3.
The allophanic acid ester-formin of polyisocyanates is, for example, that Takenate D-178N (are above the chemical (strain of Mitsui
Formula commercial firm) manufacture) etc..
Alkyl is, for example,：Straight chained alkyl, branched alkyl, naphthenic base etc..
The carbon number of alkyl is not particularly limited, the upper limit is, for example, 30,29,25,20,15,12,10,9,8,7,6,5,4,
3,2 etc., lower limit is, for example, 29,25,20,15,12,10,9,8,7,6,5,4,3,2,1 etc..In one embodiment, alkyl
Carbon number is preferably 1~30, more preferably 1~20, further preferably 1~16, particularly preferably 1~12.
Straight chained alkyl is, for example,：Methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, just
Nonyl, positive decyl etc..
Branched alkyl is, for example,：Isopropyl, isobutyl group, isopentyl, isohesyl, isodecyl etc..
Naphthenic base is, for example,：Cyclopenta, cyclohexyl, suberyl etc..In addition, naphthenic base can also be one on each ring with
On hydrogen replaced by straight chained alkyl (group etc. of aforementioned illustration) or branched alkyl (group etc. of aforementioned illustration).
(polyisocyanates without aromatic group as addition forms)
The polyisocyanates without aromatic group as addition forms is, for example,：Straight-chain aliphatic polyisocyanic acid
Ester, branched aliphatic polyisocyanates and/or alicyclic polyisocyanates are through polyalcohol modified modified form etc..
Above-mentioned polyhydric alcohols are in this way：(poly-) pentaerythrite, (poly-) trimethylolpropane, (poly-) glycerine, D-sorbite, sugar
Deng.
The addition forms of polyisocyanates are, for example,：
By the addition forms of trimethylolpropane and polyisocyanates that following structural formula (A-4) indicates：
[changing 4]
In formula, R4A~R4EIt is each independently alkyl, R4D~R4EGroup can be different for each structural unit；n4
It is 0 or more integer, n4 is preferably 0~3；Or
By the addition forms etc. of glycerine and polyisocyanates that following structural formula (A-5) indicates：
[changing 5]
In formula, R5A~R5EIt is each independently alkyl, R5D~R5EGroup can be different for each structural unit；n5
It is 0 or more integer, n5 is preferably 0~3.
The addition forms of polyisocyanates are, for example,：Duranate P301-75E are (above for Japanese Asahi Chemical Industry (strain formula
Commercial firm) manufacture), Takenate D160N (being above Mitsui chemical (Co., Ltd.) manufacture) etc..
In addition, structure above (A-1)~(A-5) is only an example, the present invention is not intended to be limited to by above-mentioned knot
The compound that structure formula indicates.
The upper limit of the weight average molecular weight (Mw) of polyisocyanates (A) is, for example, 80000,70000,60000,50000,
40000,30000,20000,10000,9000,8000,7000,6000,5000,4000,3000,2000,1000,500 etc., under
Limit be, for example, 70000,60000,50000,40000,30000,20000,10000,9000,8000,7000,6000,5000,
4000,3000,2000,1000,500,300 etc..In one embodiment, from the life of carbamate (methyl) acrylate
From the viewpoint of production property, the weight average molecular weight (Mw) of polyisocyanates (A) is preferably 300~80000.
The upper limit of the number-average molecular weight (Mn) of polyisocyanates (A) is, for example, 60000,55000,50000,40000,
30000,20000,10000,9000,8000,7000,6000,5000,4000,3000,2000,1000,500,300 etc., lower limit
E.g. 55000,50000,40000,30000,20000,10000,9000,8000,7000,6000,5000,4000,3000,
2000,1000,500,300,200 etc..In one embodiment, from the productive of carbamate (methyl) acrylate
From the point of view of viewpoint, the number-average molecular weight (Mn) of polyisocyanates (A) is preferably 200~60000.
The upper limit of the molecular weight distribution (Mw/Mn) of polyisocyanates (A) is, for example, 8.0,7.0,6.0,5.0,4.0,3.0,
2.0 etc., lower limit is, for example, 7.0,6.0,5.0,4.0,3.0,2.0,1.0 etc..In one embodiment, from carbamate
From the viewpoint of the productivity of (methyl) acrylate, the molecular weight distribution (Mw/Mn) of polyisocyanates (A) is preferably 1.0~
8.0。
Weight average molecular weight (Mw) and number-average molecular weight (Mn) can be poly- as being measured by gel permeation chromatography (GPC)
Styrene equivalent value is found out (the same below).
Relative to 100 mass parts of above compound group, the upper limit of the ratio of polyisocyanates (A) is, for example, 50,40,30,
20,10 mass parts etc., lower limit are, for example, 45,40,30,20,10,5 mass parts etc..In one embodiment, from taking into account anti-scratch
From the viewpoint of wound property and hardness, low crimpiness, relative to 100 mass parts of above compound group, the ratio of polyisocyanates (A)
Preferably 5~50 mass parts.
<More (methyl) acrylate (B) of polypentaerythritol containing hydroxyl：Also referred to as (B) ingredient>
More (methyl) acrylate of polypentaerythritol containing hydroxyl are the compounds indicated by the following general formula (1)：
[changing 6]
In formula, n is 2 or more integer (such as 2,3,4,5 etc.)；R1~R6It is each independently hydrogen or (alkylene oxide (ア Le
キ レ Application オ キ サ イ De) modification of modified or epoxy (エ Port キ シ)) (methyl) acryloyl group, but at least one is hydrogen；In addition,
R3And R5Group can be different for each structural unit.
In the present invention, refer to " with polypentaerythritol skeleton more than tripolymer " for example in general formula (1) n be 2 with
On.
In the present invention, " for each structural unit group can different " refer to for example in the case of general formula (1),
When n is 2,
[changing 7]
R3AWith R3BIt can be different group, R5AWith R5BIt can be different group.
More (methyl) acrylate (B) of polypentaerythritol containing hydroxyl can be by the various well known poly- seasons containing hydroxyl
More (methyl) acrylate of penta tetrol are used alone, and can also use two or more merging.With poly- season more than tripolymer
More (methyl) acrylate of the polypentaerythritol containing hydroxyl of penta 4 ol skeletons are, for example,：(alkylene oxide changes tripentaerythritol two
Property is epoxy-modified) (methyl) acrylate, tripentaerythritol three (alkylen oxide-modified or epoxy-modified) (methyl) acrylate,
Tripentaerythritol four (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, (the alkylen oxide-modified or ring of tripentaerythritol five
Oxygen be modified) (methyl) acrylate, tripentaerythritol six (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, three seasons penta
Tetrol seven (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetrapentaerythritol two (alkylen oxide-modified or epoxy-modified)
(methyl) acrylate, tetrapentaerythritol three (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetrapentaerythritol four
(alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetrapentaerythritol five (alkylen oxide-modified or epoxy-modified) (methyl)
Acrylate, tetrapentaerythritol six (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, seven (alkylene oxide of tetrapentaerythritol
It is modified or epoxy-modified) (methyl) acrylate, tetrapentaerythritol eight (alkylen oxide-modified or epoxy-modified) (methyl) acrylic acid
Ester, tetrapentaerythritol nine (alkylen oxide-modified or epoxy-modified) (methyl) acrylate etc..
In the present invention, " (alkylen oxide-modified or epoxy-modified) (methyl) acrylate " refers to " selected from by (methyl)
At least one in the group of acrylate, alkylen oxide-modified (methyl) acrylate and epoxy-modified (methyl) acrylate composition
Kind ".
It is alkylen oxide-modified to be, for example,：Ethylene-oxide-modified, epoxy pronane modification etc..
The upper limit of the hydroxyl value of more (methyl) acrylate (B) of polypentaerythritol containing hydroxyl is, for example, 80,75,70,65,
60,55,50,45,40,35,30,25,20mgKOH/g etc., lower limit is, for example, 75,70,65,60,55,50,45,40,35,30,
25,20,15mgKOH/g etc..In one embodiment, from the viewpoint of taking into account marresistance and hardness, low crimpiness, contain
It is preferably 15~80mgKOH/g to have the hydroxyl value of more (methyl) acrylate (B) of the polypentaerythritol of hydroxyl, more preferably 25~
80mgKOH/g。
In the present invention, hydroxyl value refers to the calculated value obtained by following formula：
(hydroxyl value)=(potassium hydroxide molecular weight：56.1) × 1000/ (hydroxyl equivalent)；
(hydroxyl equivalent)=(molecular weight of 1 molecule)/(hydroxyl value present in 1 molecule).
The upper limit of (methyl) acrylic equivalent of more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl is, for example,
150,140,130,120,110g/eq etc., lower limit is, for example, 140,130,120,110,100g/eq etc..In an embodiment
In, from the viewpoint of hardness and marresistance, (methyl) of more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
Acrylic equivalent is preferably 100~150g/eq.
In the present invention, " (methyl) acrylic equivalent " refers to the molecular weight of every mole of (methyl) acryloyl group, is passed through
Following formula is found out：
((methyl) acrylic equivalent)=(molecular weight of 1 molecule)/((methyl) acryloyl present in 1 molecule
Radix).
Relative to 100 mass parts of above compound group, more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
The upper limit of ratio is, for example, 95,90,80,70,60,55 mass parts etc., and lower limit is, for example, 90,80,70,60,55,50 mass parts
Deng.In one embodiment, from the viewpoint of hardness and marresistance, relative to 100 mass parts of compound group, contain hydroxyl
The ratio of more (methyl) acrylate (B) of polypentaerythritol of base is preferably 50~95 mass parts.
<Neither (A) ingredient nor (B) ingredient compound：Also referred to as other compounds>
When manufacturing above-mentioned carbamate (methyl) acrylate (1), can use neither (A) ingredient nor
(B) compound of ingredient.That is, in above compound group, can contain neither (A) ingredient nor (B) ingredient chemical combination
Object.Neither (A) ingredient is nor the compound of (B) ingredient is, for example,：It is not the isocyanates of (A) ingredient, is not (B) ingredient
(methyl) acrylate containing hydroxyl etc..
The isocyanates for not being (A) ingredient is, for example, monoisocyanates, the polyisocyanates containing aromatic group, does not have
By in the group being made of isocyanurate group, biuret groups and allophanate group group, be not addition forms
Polyisocyanates (also referred to as non-modified polyisocyanates).
Non-modified polyisocyanates is, for example,：Above-mentioned straight-chain aliphatic polyisocyanates, branched aliphatic polyisocyanates,
Alicyclic polyisocyanates etc..
(methyl) acrylate containing hydroxyl for not being (B) ingredient is, for example,：Glycerine (methyl) propylene containing hydroxyl
More (methyl) acrylate of acid esters, the pentaerythrite containing hydroxyl, more (methyl) acrylate of the dipentaerythritol containing hydroxyl,
More (methyl) acrylate of (poly-) trimethylolpropane containing hydroxyl, simple function (methyl) acrylate etc. containing hydroxyl.
In one embodiment, relative to 100 mass % of above compound group, the ratio of other compounds is, for example,：0
~50 mass %, it is less than 40 mass %, is less than 25 mass %, is less than 10 mass %, is less than 5 mass %, is less than 1 mass %, is small
In 0.1 mass %, less than 0.01 mass %, 0 mass % etc..
In one embodiment, relative to 100 moles of % of above compound group, the ratio of other compounds is, for example,：0
~50 moles of %, it is less than 40 moles of %, is less than 25 moles of %, is less than 10 moles of %, is less than 5 moles of %, is less than 1 mole of %, is small
In 0.1 mole of %, less than 0.01 mole of %, 0 mole of % etc..
Well known method may be used in the manufacturing method of above-mentioned carbamate (methyl) acrylate, can make (A) at
Divide and (B) ingredient is in solvent solvent-free or appropriate (toluene etc.), in the presence of catalyst appropriate (tin octoate etc.), with
Reaction temperature (60~90 DEG C etc.) appropriate is reacted.
<The relative scale of each ingredient>
Mass ratio (the polyisocyanate cyanogen of polyisocyanates (A) and more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
More (methyl) acrylate (B) of acid esters (A)/polypentaerythritol containing hydroxyl) the upper limit be, for example, 6,5,4,3,2,1,0.9,
0.5,0.4,0.2,0.1 etc., lower limit is, for example, 5,4,3,2,1,0.9,0.5,0.4,0.2,0.1,0.05 etc..In an embodiment party
In formula, from the viewpoint of taking into account marresistance and hardness, low crimpiness, polyisocyanates (A) and the poly- season penta containing hydroxyl
Mass ratio (polyisocyanates (A)/polypentaerythritol containing hydroxyl more (methyl) third of more (methyl) acrylate (B) of tetrol
Olefin(e) acid ester (B)) it is preferably 0.05~6.
The upper limit of the mass ratio (other compound/polyisocyanates (A)) of other compounds and polyisocyanates (A) is for example
It is 10,9,7.5,5,2.5,1,0.5 etc., lower limit is, for example, 9,7.5,5,2.5,1,0.5,0 etc..In one embodiment,
Its compound and the mass ratio (other compound/polyisocyanates (A)) of polyisocyanates (A) are preferably 0~10.
Mass ratio (other chemical combination of other compounds and more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
More (methyl) acrylate (B) of object/polypentaerythritol containing hydroxyl) the upper limit be, for example, 1,0.9,0.75,0.5,0.25,
0.1,0.05 etc., lower limit is, for example, 0.9,0.75,0.5,0.25,0.1,0.05,0 etc..In one embodiment, other chemical combination
Mass ratio (other compounds/poly- the season containing hydroxyl of object and more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
More (methyl) acrylate (B) of penta tetrol) it is preferably 0~1.
The isocyanic acid of the hydroxyl and polyisocyanates (A) of more (methyl) acrylate (B) of polypentaerythritol containing hydroxyl
The upper limit of the ratio between amount of substance of ester group [(OH)/(NCO)] is, for example, 2.5,2.0,1.5,1.0 etc., lower limit is, for example, 2.4,
2.0,1.5,1.0,0.95 etc..In one embodiment, the polypentaerythritol containing hydroxyl more (methyl) acrylate (B)
The ratio between hydroxyl and the amount of substance of isocyanate group of polyisocyanates (A) [(OH)/(NCO)] are preferably 0.95~2.5.
<The physical property etc. of carbamate (methyl) acrylate>
The upper limit of the weight average molecular weight (Mw) of above-mentioned carbamate (methyl) acrylate is, for example, 80000,70000,
60000,50000,40000,30000,20000,10000,9000,8000,7000,6000,5000,4000,3000 etc., lower limit
E.g. 70000,60000,50000,40000,30000,20000,10000,9000,8000,7000,6000,5000,
4000,3000,2000 etc..In one embodiment, from the productive sight of carbamate (methyl) acrylate and film
From the point of view of point, the weight average molecular weight (Mw) of above-mentioned carbamate (methyl) acrylate is preferably 2000~80000.
The upper limit of the number-average molecular weight (Mn) of above-mentioned carbamate (methyl) acrylate is, for example, 80000,70000,
60000、50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、4000、3000、2000
Be, for example, 70000 Deng, lower limit, 60000,50000,40000,30000,20000,10000,9000,8000,7000,6000,
5000,4000,3000,2000,1000 etc..In one embodiment, from carbamate (methyl) acrylate and film
From the viewpoint of productivity, the number-average molecular weight (Mn) of above-mentioned carbamate (methyl) acrylate is preferably 1000~
80000。
The upper limit of the molecular weight distribution (Mw/Mn) of above-mentioned carbamate (methyl) acrylate is, for example, 8.0,7.0,
6.0,5.0,4.0,3.0,2.0 etc., lower limit is, for example, 7.0,6.0,5.0,4.0,3.0,2.0,1.0 etc..In an embodiment
In, from the productivity of carbamate (methyl) acrylate and film from the viewpoint of, above-mentioned carbamate (methyl) propylene
The molecular weight distribution (Mw/Mn) of acid esters is preferably 1.0~8.0.
The upper limit of (methyl) acrylic equivalent of above-mentioned carbamate (methyl) acrylate is, for example, 300,290,
275,250,225,200,175,150,140g/eq etc., lower limit is, for example, 290,275,250,225,200,175,150,140,
130g/eq etc..In one embodiment, (methyl) acrylic equivalent of above-mentioned carbamate (methyl) acrylate is preferred
For 130~300g/eq.
[activity energy-line solidifying type resin composition：Also referred to as composition]
The present invention provides the active energy ray-curable resin combination containing above-mentioned carbamate (methyl) acrylate
Object.
Relative to 100 mass parts of above-mentioned composition, the upper limit example of the content of above-mentioned carbamate (methyl) acrylate
100,90,80,70,60,50,40,30,20 mass parts in this way etc., lower limit is, for example, 90,80,70,60,50,40,30,20,10
Mass parts etc..In one embodiment, from the viewpoint of taking into account marresistance and hardness, low crimpiness, relative to above-mentioned
The content of 100 mass parts of composition, above-mentioned carbamate (methyl) acrylate is preferably 10~100 mass parts.
<Photoepolymerizationinitiater initiater>
In one embodiment, above-mentioned activity energy-line solidifying type resin composition contains Photoepolymerizationinitiater initiater.Light is poly-
Closing initiator, various well known Photoepolymerizationinitiater initiaters can be used alone, and can also use two or more merging.In addition, light
Polymerization initiator is used in the case where carrying out ultraviolet curing, however, in the case where carrying out electronic beam curing, photopolymerization is drawn
Hair agent is not required.
Photoepolymerizationinitiater initiater is, for example,：1- hydroxy-cyclohexyl-phenyls ketone, 2,2- dimethoxy -1,2- diphenylethanes -
1- ketone, 1- cyclohexyl-phenyl ketones, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -
2- hydroxy-2-methyl -1- propane -1- ketone, 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, 2,4,6-
Trimethylbenzoy-dipheny-phosphine oxide, 4- methyl benzophenones etc..
Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of Photoepolymerizationinitiater initiater is, for example, 10,9,8,7,6,5,
4,3,2,1 mass parts etc., lower limit are, for example, 9,8,7,6,5,4,3,2,1,0.5,0 mass parts etc..In one embodiment, from
From the viewpoint of the reaction of (methyl) acryloyl group carries out, relative to 100 mass parts of above-mentioned composition, Photoepolymerizationinitiater initiater contains
Amount is preferably 0~10 mass parts.
Relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the upper limit of the content of Photoepolymerizationinitiater initiater
E.g. 66.7,65,60,55,50,45,40,35,30,25,20,15,10,9,8,7,6,5,4,3,2,1 mass parts etc., lower limit
E.g. 65,60,55,50,45,40,35,30,25,20,15,10,9,8,7,6,5,4,3,2,1,0.5,0 mass parts etc..?
In one embodiment, from the viewpoint of the reaction of (methyl) acryloyl group progress, relative to above-mentioned carbamate (first
Base) 100 mass parts of acrylate, the content of Photoepolymerizationinitiater initiater is preferably 0~66.7 mass parts.
<Polymerizable monomer>
In one embodiment, above-mentioned activity energy-line solidifying type resin composition contains polymerizable monomer.Polymerism
Various well known polymerizable monomers can be used alone for monomer, can also use two or more merging.
Polymerizable monomer is, for example,：Isobornyl (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetrahydrochysene chaff
Base (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, ethoxy (alkylen oxide-modified or epoxy-modified) (methyl) propylene
Acid esters, hydroxypropyl (methyl) acrylate, 4- hydroxyls butyl (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, lauryl
(alkylen oxide-modified or epoxy-modified) (methyl) acrylate, 1,4- butanediols two (alkylen oxide-modified or epoxy-modified) (methyl)
Acrylate, 1,6-HD two (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, (alkylene oxide changes tetraethylene glycol two
Property is epoxy-modified) (methyl) acrylate, tripropylene glycol two (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, three
Hydroxymethyl-propane three (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, (the alkylen oxide-modified or epoxy of pentaerythrite three
It is modified) (methyl) acrylate, pentaerythrite four (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, dipentaerythritol
Five (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, dipentaerythritol six (alkylen oxide-modified or epoxy-modified) (first
Base) acrylate, tripentaerythritol eight (alkylen oxide-modified or epoxy-modified) (methyl) acrylate etc..
In the present invention, " (alkylen oxide-modified or epoxy-modified) (methyl) acrylate " refers to " selected from by (methyl)
At least one in the group of acrylate, alkylen oxide-modified (methyl) acrylate and epoxy-modified (methyl) acrylate composition
Kind ".
Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of polymerizable monomer is, for example, 85,80,75,70,65,
60,55,50,45,40,35,30,25,20,15,10,5 mass parts etc., lower limit is, for example, 80,75,70,65,60,55,50,45,
40,35,30,25,20,15,10,5,0 mass parts etc..In one embodiment, from taking into account marresistance and hardness, low curling
From the viewpoint of property, relative to 100 mass parts of above-mentioned composition, the content of polymerizable monomer is preferably 0~85 mass parts etc..
Relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the upper limit example of the content of polymerizable monomer
567,550,500,450,400,350,300,250,200,150,100,50,25,10,5,1 mass parts in this way etc., lower limit is for example
It is 550,500,450,400,350,300,250,200,150,100,50,25,10,5,1,0 mass parts etc..In an embodiment party
In formula, from the viewpoint of taking into account marresistance and hardness, low crimpiness, relative to above-mentioned carbamate (methyl) acrylic acid
The content of 100 mass parts of ester, polymerizable monomer is preferably 0~567 mass parts etc..
<Retarder thinner>
In one embodiment, above-mentioned composition contains retarder thinner.Retarder thinner can be by various well known dilutions
Solvent is used alone, and can also use two or more merging.In addition, retarder thinner is preferably ultraviolet light non-reactive solvent,
Ultraviolet light non-reactive solvent is the solvent of (polymerization) of not reacting irradiating ultraviolet light.
Retarder thinner is, for example,：Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, butyl acetate, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, diacetone alcohol, acetylacetone,2,4-pentanedione, toluene, dimethylbenzene, n-hexane, ring
Hexane, hexahydrotoluene, normal heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve ,-dioxane of Isosorbide-5-Nitrae (Isosorbide-5-Nitrae-ジ オ キ サ
Application), propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate etc..
Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of retarder thinner is, for example, 1900,1750,1500,
1250,1000,750,500,250,100,50,25 mass parts etc., lower limit is, for example, 1750,1500,1250,1000,750,
500,250,100,50,25,0 mass parts etc..In one embodiment, from the viewpoint of coating, relative to composition
The content of 100 mass parts, retarder thinner is, for example, 0~1900 mass parts etc..
Relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the upper limit of the content of retarder thinner is for example
1900,1750,1500,1250,1000,750,500,250,100,50,25 mass parts etc., lower limit is, for example, 1750,1500,
1250,1000,750,500,250,100,50,25,0 mass parts etc..In one embodiment, come from the viewpoint of coating
It sees, relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the content of retarder thinner is, for example, 0~1900 matter
Measure part etc..
<Additive>
Above-mentioned activity energy-line solidifying type resin composition can contain except above-mentioned carbamate (methyl) acrylate,
Reagent other than Photoepolymerizationinitiater initiater, polymerizable monomer, retarder thinner is as additive.
Additive is, for example,：It is antioxidant, ultra-violet absorber, light stabilizer, antifoaming agent, surface conditioner, anti-pollution
Agent, pigment, antistatic agent, metal oxide microparticle dispersion, organic fine particles dispersion etc..
In one embodiment, relative to 100 mass parts of composition, the content of additive is, for example,：0.05~50 matter
Part is measured, is less than 40 mass parts, is less than 25 mass parts, is less than 10 mass parts, is less than 5 mass parts, is less than 1 mass parts, is less than 0.1 matter
Measure part, be less than 0.01 mass parts, 0 mass parts etc..
In another embodiment, relative to 100 mass parts of carbamate (methyl) acrylate, additive contains
Amount is, for example,：0.05~333 mass parts are less than 300 mass parts, are less than 200 mass parts, are less than 100 mass parts, are less than 50 mass
Part, be less than 25 mass parts, be less than 10 mass parts, be less than 5 mass parts, be less than 1 mass parts, be less than 0.1 mass parts, be less than 0.01 matter
Measure part, 0 mass parts etc..
Above-mentioned composition by by above-mentioned carbamate (methyl) acrylate and polymerization initiator as needed,
Polymerizable monomer, retarder thinner and additive etc. are obtained by mixing using various well known methods.
Above-mentioned activity energy-line solidifying type resin composition can be used as coating agent, film coating agent, plastic sheet coating
The uses such as agent.Film is, for example, with coating agent：Tri acetyl cellulose membrane (TAC film) coating agent, acrylic film coating agent, cyclenes
Hydrocarbon resin film (COP films) coating agent etc..
[solidfied material]
The present invention provides the solidfied material of above-mentioned activity energy-line solidifying type resin composition.Above-mentioned solidfied material is by above-mentioned
Activity energy-line solidifying type resin composition irradiation ultraviolet light, electron beam, radioactive ray isoreactivity energy line and obtain.
The active energy ray used in curing reaction is, for example, ultraviolet light and electron beam.The light source of ultraviolet light is, for example, to have
There is the ultraviolet lamp etc. of xenon lamp, high-pressure sodium lamp, metal halide lamp.In addition, the configuration of light quantity, light source, conveying speed etc.
It can be adjusted as needed, using high-pressure sodium lamp, there is 80~160W/cm or so light quantity relative to every
Lamp, preferably be allowed to cure within 5~50m/ minutes or so with conveying speed.On the other hand, in the case of electron beam, with 10
In the electron beam accelerator of the accelerating potential of~300kV or so, preferably it is allowed within 5~50m/ minutes or so solid with conveying speed
Change.
[film]
The present invention provides the film containing above-mentioned solidfied material.Above-mentioned film is wanted using above-mentioned solidfied material and various basement membranes as being constituted
The article of element.
Basement membrane can use various well known basement membranes, e.g.：Polycarbonate membrane, acrylic film (poly-methyl methacrylate
Ester film etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melmac film, tri acetyl cellulose membrane,
ABS films, AS films, norbornene resin film, cycloolefin film, polyvinyl alcohol film etc..The thickness of basement membrane is not particularly limited, preferably
It is 15~100 μm or so.
Above-mentioned film can use various well known methods to manufacture.Specifically, by above-mentioned active energy ray-curable resin
Composition is coated on at least single side of above-mentioned basement membrane, is dried as needed, and active energy ray is then irradiated.Separately
Outside, resin combination of the present embodiment can also be coated on the non-coated face of obtained basement membrane, be bonded on it
Then other basement membranes irradiate active energy ray, thus manufacture laminated film.These films all can serve as optical film use.
Painting method is, for example,：Metering bar coater coating, coiling bar coating (ワ イ ヤ ー バ ー Tu works), Meyer rod coatings
Cover, air knife coating, rotogravure application, reversed rotogravure application, hectographic printing, flexible version printing (Off レ キ ソ printings), silk-screen printing
Method etc..
Coated weight is not particularly limited, and the quality after drying is preferably 0.1~30g/m2, more preferably 1~20g/m2。
Embodiment
Hereafter the present invention is concretely demonstrated by embodiment and comparative example.But in above-mentioned preferred embodiment
Explanation and following embodiment merely to citing purpose and provide, be not to be carried to limit the purpose of the present invention
For.Therefore, the embodiment that the scope of the present invention is specifically recorded neither in by this specification is limited, and is not also had in by this specification
The embodiment that body is recorded limits, and the scope of the present invention is only limited by the range of claims.Meanwhile as long as no especially saying
Bright, in each embodiment and comparative example, the numerical value of part, % etc. are quality criteria.
(weight average molecular weight)
It is manufactured by gel permeation chromatography (this East ソ ー (Co., Ltd.), trade name " HLC-8220 "；Column：This East of
ソ ー (Co., Ltd.) are manufactured, and are measured obtained by trade name " TSKgel superHZ2000 ", " TSKgel superHZM-M "
Value.
(manufacture of active energy ray-curable resin)
Embodiment 1
Hexa-methylene two is loaded in the reaction vessel for having agitating device, cooling tube, dropping funel and nitrogen ingress pipe
193 parts of isocyanurate-modified object (Coronate HXR, this East ソ ー (Co., Ltd.) manufactures), the tin octoate of isocyanates
0.6 part, raw material (Viscoat#802 (ビ ス コ ー ト #802), hydroxyl value containing the more acrylate forms of tripentaerythritol
Form=10~20/55~65/5~15 of the form of 36mgKOH/g, two or five forms/tri- or five/tetra- or five, Osaka, Japan organic chemistry work
Industry company manufactures) after 1560 parts, the temperature in system is warming up to about 80 DEG C by about 1 hour.Then, by reaction system in phase
It is cooling after synthermal lower holding 2 hours, obtain the mixture of carbamate (methyl) acrylate (A-1) and residual monomer.
Weight average molecular weight is 10800.Coordinate 1- hydroxy-cyclohexyl-phenyls according to solid constituent ratio relative to 100 parts of the mixture
Ketone (BASF Japan (Co., Ltd.) manufacture, trade name " IRGACURE184 (イ Le ガ キ ュ ア ー 184) ", hereinafter referred to as
HCPK it) 5 parts, is diluted using the mixed solvent of methyl ethyl ketone/methyl iso-butyl ketone (MIBK)=6/4, prepares nonvolatile component
40% active energy ray-curable composition.
For embodiment 2~7, comparative example 1~7, other than changing ingredient recorded in following tables, with reality
The equally operation of example 1 is applied to implement.
Embodiment 8
Relative to obtained 80 parts of (A-2) ingredient of embodiment 2, according to solid constituent ratio, cooperation is used as other ingredients
20 parts of dipentaerythritol hexaacrylate Dipentaerythritol Pentaacrylate mixture (ア ロ ニ ッ Network ス M-400, Japan
East Asia Synesis Company manufacture), 5 parts of HCPK, using methyl ethyl ketone/methyl iso-butyl ketone (MIBK)=6/4 mixed solvent carry out it is dilute
It releases, prepares the active energy ray-curable composition of nonvolatile component 40%.
For embodiment 9, other than changing the ingredient recorded in table 1, operation similarly to Example 8 is implemented.
<The making of solidfied material>
On the tri acetyl cellulose membrane of 60 μm of film thickness, each activity energy-line solidifying type resin composition is scraped using #14
Rod coater is coated, and it is 7 μm to make the film thickness of film after solidification, is allowed at 70 DEG C dry 1 minute to make film.Then, will
Obtained film uses ultraviolet curing device (product name：UBT-080-7A/BM, Japan (Co., Ltd.) マ Le チ プ ラ イ systems
It makes, high-pressure sodium lamp 600mJ/cm2)) processing, obtain the film containing solidfied material.
For embodiment 2~9 and comparative example 1~7, film is equally made, solidfied material is evaluated as described below.As a result show
In following tables.
Hardness (pencil hardness)
According to JIS K5600-5-4, the hardness of solidfied material is evaluated by the pencil test of loading 500g.
Low crimpiness
Film is cut into 10cm × 10cm, is not as the case where tubular (situation that the end of film overlaps each other) according to film
"○" is classified as the case where tubular for "×".
Marresistance
It is past relative to film using the weight (weight り) for the 1500g that steel wool (#0000,10mm × 10mm) is pasted onto to bottom
Friction 10 times is returned, visual assessment appearance of film is carried out according to following benchmark.
○：There is no the variation of the appearance of films such as scratch or albefaction；
×：There is the variation of the appearance of films such as scratch or albefaction.
Light resistance
In ultraviolet light self-discoloration instrument (trade name：Ultraviolet light self-discoloration instrument U48AU, Japanese ス ガ testing machines (strain formula meeting
Society) manufacture) in, film is exposed 100 hours with carbon arc lamp.Film after experiment passes through colour difference meter (trade name：ZE 6000, Japan's electricity
Color industry (Co., Ltd.) manufacture) penetrant method be measured, if exposure after yellow colour index value (イ エ ロ ー イ Application デ ッ
Network ス values) be less than 2, then it is classified as "○"；If 2 or more, it is classified as "×".
[table 1]
[table 2]
Coronate HXR：Isocyanurate-modified object (this East ソ ー (strain formula meetings of hexamethylene diisocyanate
Society) manufacture)
Duranate 24A-100：Biuret modified object (Japanese Asahi Chemical Industry's (strain formula meeting of hexamethylene diisocyanate
Society) manufacture)
Takenate D-178N：The allophanate-modified object mixture (Mitsui of hexamethylene diisocyanate
Learn (Co., Ltd.) manufacture)
Takenate D-127N：Isocyanurate-modified object (the Mitsui chemistry of hydrogenated xylene diisocyanate
(Co., Ltd.) manufactures)
VESTANAT T1890/100：Isocyanurate-modified object (the SUMITOMO CHEMICAL バ イ of isophorone diisocyanate
エ Le ウ レ タ Application (Co., Ltd.) manufactures)
Takenate 600：Hydrogenated xylene diisocyanate (Mitsui chemistry (Co., Ltd.) manufacture)
Coronate 2030：Isocyanurate-modified object (this East ソ ー (Co., Ltd.) of toluene di-isocyanate(TDI) are made
It makes)
Duranate E402-90T：Addition forms (the Japanese Asahi Chemical Industry (Co., Ltd.) of hexamethylene diisocyanate
Manufacture)
Viscoat#802：Raw material (hydroxyl value 36mgKOH/g, two or five shapes containing the more acrylate forms of tripentaerythritol
Form=10~20/55~65/5~15 of the form of formula/tri- or five/tetra- or five, Osaka, Japan Organic Chemical Industry (Co., Ltd.) manufacture)
アロニックスM-400：Dipentaerythritol hexaacrylate Dipentaerythritol Pentaacrylate mixture (day
This East Asia synthesizes (Co., Ltd.) manufacture)
HCPK：1- hydroxy-cyclohexyl-phenyls ketone (BASF Japan (Co., Ltd.) manufacture, trade name " IRGACURE184 ")
Claims (5)
1. carbamate (methyl) acrylate, carbamate (methyl) acrylate is the change containing following compositions
Close the reaction product of object group：
Polyisocyanates (A) without aromatic group, the polyisocyanates (A) without aromatic group, which has, to be selected from
At least one of the group being made of isocyanurate group, biuret groups and allophanate group group and/or it is described without virtue
The polyisocyanates (A) of fragrant race's group is addition forms；And
More (methyl) acrylate (B) of polypentaerythritol, more (methyl) acrylate (B) of polypentaerythritol have tripolymer
Above polypentaerythritol skeleton simultaneously contains hydroxyl.
2. the active energy ray-curable resin combination containing carbamate as described in claim 1 (methyl) acrylate
Object.
3. activity energy-line solidifying type resin composition as claimed in claim 2, the active energy ray-curable resin group
It closes object and contains Photoepolymerizationinitiater initiater.
4. the solidfied material of activity energy-line solidifying type resin composition as claimed in claim 2 or claim 3.
5. the film containing solidfied material as claimed in claim 4.
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| JP2017079977 | 2017-04-13 | ||
| JP2017-079977 | 2017-04-13 |
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| JP (1) | JP6870648B2 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239599A (en) * | 2019-07-16 | 2021-01-19 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film |
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- 2018-04-12 JP JP2018076614A patent/JP6870648B2/en active Active
- 2018-04-12 TW TW107112607A patent/TWI737908B/en active
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| JPH0539343A (en) * | 1991-06-17 | 1993-02-19 | Koei Chem Co Ltd | Production of urethane (meth)acrylate oligomer and photocurable resin composition produced therefrom |
| EP0543393A1 (en) * | 1991-11-21 | 1993-05-26 | Mitsubishi Rayon Co., Ltd | Coating composition |
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| JP2015067699A (en) * | 2013-09-27 | 2015-04-13 | 株式会社日本触媒 | Curable resin composition and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112239599A (en) * | 2019-07-16 | 2021-01-19 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film |
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| Publication number | Publication date |
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| CN108727556B (en) | 2021-08-17 |
| JP2018178114A (en) | 2018-11-15 |
| TW201843204A (en) | 2018-12-16 |
| JP6870648B2 (en) | 2021-05-12 |
| KR102325929B1 (en) | 2021-11-11 |
| KR20180115648A (en) | 2018-10-23 |
| TWI737908B (en) | 2021-09-01 |
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