CN109096469A - Carbamate (methyl) acrylate, actinic energy ray curable resion composition, solidfied material and protective film - Google Patents
Carbamate (methyl) acrylate, actinic energy ray curable resion composition, solidfied material and protective film Download PDFInfo
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- 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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- 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
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
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- 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
- C08G18/6715—Unsaturated monofunctional alcohols or amines
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- 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
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
Abstract
The purpose of the present invention is to provide a kind of carbamate (methyl) acrylate, actinic energy ray curable resion composition, solidfied material and protective films.The present invention provides a kind of carbamate (methyl) acrylate, it is obtained from so that monomer group is reacted, the monomer group includes representative examples of saturated aliphatic polyisocyanates, representative examples of saturated aliphatic polyalcohol, polyether polyol and/or polyester polyol, and (methyl) acrylate of hydroxyl, relative to above-mentioned 100 mass parts of monomer group, include the above-mentioned polyether polyol of 0.2 mass parts~10 mass parts and/or above-mentioned polyester polyol, relative to 100 mass parts of carbamate (methyl) acrylate, include 19 mass parts~48 mass parts cycloalkylidene.
Description
Technical field
This application involves carbamate (methyl) acrylate, actinic energy ray curable resion composition, solidification
Object and protective film.
Background technique
The light weight of plastics and have excellent processability, is used in various fields.But the most penetrability of plastics
Height, such as in the case wheres the protection etc. for electronic equipment etc., it is easy to happen failure because of contact with moisture electronic equipment, because
This, has carried out various researchs to inhibit penetrability.As 1 of the studies above, proposes to be formed in frosting and protect
The method of film.
Summary of the invention
Problems to be solved by the invention
However, the thickness of protective film is thinner, then moisture more readily penetrates through protective film (moisture permeability is got higher), and accordingly, there exist patches
Together in protective film plastics be easy moisture absorption dehumidification the problem of.In recent years, it is desirable that further filming and low moisture-inhibiting, to 20 μm
Film below requires such as moisture permeability to reach 80g/ (m2Low-moisture permeability below for 24 hours).In addition, being deposited in the state of thin layer
It is crisp and the problem of be easily broken off, therefore, also require treatability when having obdurability, i.e. operation, the good protection of durability
Film.
The problem to be solved by the present invention is to provide can have both moisture permeability with 20 μm of film formation below as 80g/
(m2Carbamate (methyl) acrylate of the protective film of low-moisture permeability and obdurability below for 24 hours).
The method for solving problem
Further investigation has been repeated for the above subject in the inventors of the present invention, as a result, it has been found that: by using defined amino
Formic acid esters (methyl) acrylate, is capable of forming the protective film for having both low-moisture permeability and obdurability.
By the application, following projects are provided.
(project 1)
A kind of carbamate (methyl) acrylate is the reactant of monomer group, and the monomer group includes:
Representative examples of saturated aliphatic polyisocyanates,
Representative examples of saturated aliphatic polyalcohol,
Polyether polyol and/or polyester polyol and
(methyl) acrylate of hydroxyl,
Relative to above-mentioned 100 mass parts of monomer group, comprising the above-mentioned polyether polyols of 0.2 mass parts~10 mass parts it is pure and mild/
Or above-mentioned polyester polyol,
Relative to 100 mass parts of carbamate (methyl) acrylate, include the sub- ring of 19 mass parts~48 mass parts
Alkyl.
(project 2)
Carbamate (methyl) acrylate according to any one of above-mentioned project, it includes:
Following structure A from above-mentioned representative examples of saturated aliphatic polyisocyanates,
-CO-NH-R1- NH-CO- (structure A)
(in formula, R1For alkylidene or cycloalkylidene)
Following structure B from above-mentioned representative examples of saturated aliphatic polyalcohol,
-O-R2- O- (structure B)
(in formula, R2For alkylidene or cycloalkylidene)
Following structure Cs 1 from above-mentioned polyether polyol and/or following structure Cs 2 from above-mentioned polyester polyol,
[chemical formula 3]
(in formula, R3For alkylidene or cycloalkylidene, the integer that n is 2 or more),
[chemical formula 4]
(in formula, R4For alkylidene or cycloalkylidene, the integer that m is 2 or more)；And
Following structure D of (methyl) acrylate from above-mentioned hydroxyl,
-O-R5a-O-C(O)-CR5b=CH2(structure D)
(in formula, R5aFor alkylidene or cycloalkylidene, R5bFor hydrogen or methyl).
(project 3)
A kind of actinic energy ray curable resion composition, it includes the carbamic acids described in any one of above-mentioned project
Ester (methyl) acrylate.
(project 4)
A kind of solidfied material, for consolidating for actinic energy ray curable resion composition described in any one of above-mentioned project
Compound.
(project 5)
A kind of protective film, it includes the solidfied materials described in any one of above-mentioned project.
One or more above-mentioned features can be further combined to provide on the basis of published combination.This field skill
Art personnel following detailed description and are understood as desired by reading, it can be appreciated that in addition to the foregoing other
Embodiment and advantage.
The effect of invention
It is coated by using carbamate described in present embodiment (methyl) acrylate, moisture-inhibiting can be obtained
Spend protective film low, that breaking strength is high.By using said protection film, can obtain will not the performance under high temperature and humidity
Reduced barrier film, polarization plates, film for packaging etc..
Specific embodiment
Generally speaking with regard to the application, the numberical range of each physics value, content etc. can be suitably set (for example, from following each
It is selected in upper limit value and lower limit value documented by project).Specifically, being illustrated as about numerical value α in the upper limit of numerical value α
In the case that the lower limit of A1, A2, A3 etc. and numerical value α are illustrated as B1, B2, B3 etc., the range of numerical value α can exemplify A1 or less, A2
Below, 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 application provides a kind of carbamate (methyl) acrylate, is the reactant of monomer group, the monomer group
Include:
Representative examples of saturated aliphatic polyisocyanates,
Representative examples of saturated aliphatic polyalcohol,
Polyether polyol and/or polyester polyol and
(methyl) acrylate of hydroxyl,
Relative to above-mentioned 100 mass parts of monomer group, comprising the above-mentioned polyether polyols of 0.2 mass parts~10 mass parts it is pure and mild/
Or above-mentioned polyester polyol,
Relative to 100 mass parts of carbamate (methyl) acrylate, include the sub- ring of 19 mass parts~48 mass parts
Alkyl.
In the application, " (methyl) acrylate " refers to " at least 1 in acrylate and methacrylate ".
Similarly, " (methyl) acryloyl group " refers to " at least 1 in acryloyl group and methylacryloyl ".
In 1 embodiment, above-mentioned carbamate (methyl) acrylate includes:
Following structure A from representative examples of saturated aliphatic polyisocyanates,
-CO-NH-R1- NH-CO- (structure A)
(in formula, R1For alkylidene or cycloalkylidene)
Following structure B from representative examples of saturated aliphatic polyalcohol,
-O-R2- O- (structure B)
(in formula, R2For alkylidene or cycloalkylidene)
Following structure Cs 1 from polyether polyol and/or following structure Cs 2 from polyester polyol,
[chemical formula 5]
(in formula, R3For alkylidene or cycloalkylidene, the integer that n is 2 or more)
[chemical formula 6]
(in formula, R4For alkylidene or cycloalkylidene, the integer that m is 2 or more)；And
Following structure D of (methyl) acrylate from hydroxyl,
-O-R5a-O-CO-CR5b=CH2(structure D)
(in formula, R5aFor alkylidene or cycloalkylidene, R5bFor hydrogen or methyl).
<representative examples of saturated aliphatic polyisocyanates>
In the application, " representative examples of saturated aliphatic polyisocyanates " refers to comprising saturated aliphatic groups and 2 or more isocyanic acid
The compound of ester group (- N=C=O).In the application, " saturated aliphatic groups " refer to without unsaturated bonds such as double bond, three keys
Alkyl.Saturated aliphatic groups can exemplify alkyl, naphthenic base, alkylidene, cycloalkylidene etc..Representative examples of saturated aliphatic polyisocyanic acid
Ester can also be applied in combination two or more.
In 1 embodiment, representative examples of saturated aliphatic polyisocyanates is indicated with following structural formula:
O=C=N-R1’- N=C=O (structural formula A)
(in formula, R1’For alkylidene or cycloalkylidene).
Representative examples of saturated aliphatic polyisocyanates can exemplify alkylidene polyisocyanates, cycloalkylidene polyisocyanates or its add
At object, modifier etc..
The carbon number of saturated aliphatic groups is not particularly limited, the upper limit can exemplify 30,29,25,20,15,12,10,
9,8,7,6,5,4,3,2 etc., lower limit can exemplify 29,25,20,15,12,10,9,8,7,6,5,4,3,2,1 etc..Implement at 1
In mode, the carbon number of saturated aliphatic groups is preferably 1~30, is more preferably 1~20, is more preferably 1~16, especially excellent
It is selected as 1~12.
Alkylidene can exemplify straight-chain alkyl-sub, branched alkylidene etc..
Straight-chain alkyl-sub can use-(CH2)nThe general formula of (integer that n is 1 or more) indicates.Straight-chain alkyl-sub can exemplify
Methylene, ethylidene, propylidene, positive butylidene, positive pentylidene, positive hexylidene, positive heptamethylene, positive octamethylene, positive nonylene, just
Decylene etc..
Straight-chain aliphatic polyisocyanates can exemplify methylene diisocyanate, dimethylene diisocyanate, Sanya
Methyl diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, seven Asias
Methyl diisocyanate, eight methylene diisocyanates, nine methylene diisocyanates, decamethylene diisocyanate etc..
Branched alkylidene is group made of at least one hydrogen in straight-chain alkyl-sub is replaced by alkyl.Branched alkylidene can
Exemplify diethyl pentylidene, trimethyl butylidene, trimethyl pentylidene, trimethyl hexamethylene etc..
Branched aliphatic polyisocyanates can exemplify diethyl pentamethylene diisocyanate, two isocyanide of trimethyl butylidene
Acid esters, trimethyl pentamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc..
Cycloalkylidene can exemplify monocycle cycloalkylidene, crosslinking ring cycloalkylidene, fused rings cycloalkylidene etc..In addition, sub-
1 or more hydrogen in naphthenic base can optionally be replaced by straight chained alkyl or branched alkyl.
In the application, monocycle refers to that the inside formed in the covalent bond by carbon does not have the cyclic structure of cross-linked structure.
In addition, fused rings refer to that 2 or more monocycles share the ring-type on 2 atoms (that is, 1 side for only sharing (condensed) each ring each other)
Structure.Crosslinking ring refers to that 2 or more monocycles share the cyclic structure of 3 or more atoms.
Monocycle cycloalkylidene can exemplify cyclopentylene, cyclohexylidene, cycloheptylidene, sub- cyclodecyl, 3,5,5- trimethyls
Cyclohexylidene etc..
Crosslinking ring cycloalkylidene can exemplify tricyclic decylene, sub- adamantyl, sub- norborny etc..
Fused rings cycloalkylidene can exemplify bicyclic decylene etc..
Cycloalkylidene polyisocyanates can exemplify hydrogenated diphenyl methane diisocyanate (H12MDI), hydrogenated xylylen
The monocycles cycloalkylidene polyisocyanates such as diisocyanate (HXDI), isophorone diisocyanate (IPDI)；Norbornene two
Isocyanates (NBDI) etc. is crosslinked ring cycloalkylidene polyisocyanates；The fused rings cycloalkylidenes such as bicyclic decylene diisocyanate
Polyisocyanates.
Representative examples of saturated aliphatic polyisocyanates is preferably cycloalkylidene polyisocyanates, wherein is gone out from the viewpoint of low-moisture permeability
Hair, further preferably hydrogenated xylene diisocyanate (HXDI), norbornene diisocyanate (NBDI).
Relative to 100 mass parts of monomer group, the upper content limit of representative examples of saturated aliphatic polyisocyanates can exemplify 50 mass parts,
45 mass parts, 40 mass parts, 35 mass parts etc., lower limit can exemplify 45 mass parts, 40 mass parts, 35 mass parts, 30 mass parts
Deng.In 1 embodiment, relative to 100 mass parts of monomer group, the content of representative examples of saturated aliphatic polyisocyanates is preferably 30 matter
Measure part~50 mass parts.
Relative to 100 moles of % of monomer group, the upper content limit of representative examples of saturated aliphatic polyisocyanates can exemplify 50 moles of %,
45 moles of %, 40 moles of %, 35 moles of % etc., lower limit can exemplify 45 moles of %, 40 moles of %, 35 moles of %, 30 moles of %
Deng.In 1 embodiment, relative to 100 moles of % of monomer group, the content of representative examples of saturated aliphatic polyisocyanates is preferably 30 to rub
You are %~50 mole %.
In the case that representative examples of saturated aliphatic polyisocyanates is alkylidene polyisocyanates, from the viewpoint of low-moisture permeability,
The carbon number of alkylidene is preferably 6.In addition, in the case that representative examples of saturated aliphatic polyisocyanates is cycloalkylidene polyisocyanates,
From the viewpoint of low-moisture permeability, the carbon number of cycloalkylidene is preferably 6~7.
<representative examples of saturated aliphatic polyalcohol>
In the application, " representative examples of saturated aliphatic polyalcohol " refers to that 2 or more hydroxyls (hydroxyl) are bonded directly to saturated fat
The compound of race's group.Representative examples of saturated aliphatic polyalcohol can be applied in combination two or more.In 1 embodiment, aliphatic is more
First alcohol is indicated with structural formula B.
HO-R2’- OH (structural formula B)
(in formula, R2’For alkylidene or cycloalkylidene).
Representative examples of saturated aliphatic polyalcohol can exemplify alkylidene polyol, cycloalkylidene polyalcohol or its addition product, modifier
Deng.
Alkylidene polyol can exemplify straight-chain alkyl-sub polyalcohol, branched alkylen polylol etc..
Straight-chain alkyl-sub polyalcohol can exemplify ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, pungent
Glycol, nonanediol, decanediol etc..
Branched alkylen polylol can exemplify neopentyl glycol, 2,4- diethyl -1,5-PD, dibutyl -1 2,4-,
5- pentanediol, 1- Propylene Glycol, 1- ethohexadiol, trimethylolpropane, pentaerythrite etc..
Cycloalkylidene polyalcohol can exemplify monocycle cycloalkylidene polyalcohol, crosslinking ring cycloalkylidene polyalcohol etc..
Monocycle cycloalkylidene polyalcohol can exemplify Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, 2,2 '-bis- (4- hydroxyls
Butylcyclohexyl) propane etc..
Crosslinking ring cycloalkylidene polyalcohol can exemplify Tricyclodecane Dimethanol etc..
In the case that representative examples of saturated aliphatic polyalcohol is alkylidene polyol, from the viewpoint of low-moisture permeability, alkylidene
Carbon number is preferably 2~9.In addition, in the case that representative examples of saturated aliphatic polyalcohol is cycloalkylidene polyalcohol, from easy acquisition
Viewpoint is set out, and the carbon number of cycloalkylidene is preferably 6~10.
Relative to 100 mass parts of monomer group, the upper content limit of representative examples of saturated aliphatic polyalcohol can exemplify 40 mass parts, 30 matter
Part, 20 mass parts, 15 mass parts etc. are measured, lower limit can exemplify 35 mass parts, 30 mass parts, 20 mass parts, 10 mass parts etc..?
In 1 embodiment, relative to 100 mass parts of monomer group, the content of representative examples of saturated aliphatic polyalcohol is preferably 10 mass parts~40
Mass parts.
Relative to 100 moles of % of monomer group, the upper content limit of representative examples of saturated aliphatic polyalcohol can exemplify 40 moles of %, 30 and rub
Your %, 20 moles of %, 15 moles of % etc., lower limit can exemplify 35 moles of %, 30 moles of %, 20 moles of %, 10 moles of % etc..?
In 1 embodiment, relative to 100 moles of % of monomer group, the content of representative examples of saturated aliphatic polyalcohol is preferably 10 moles of %~40
Mole %.
In content of the representative examples of saturated aliphatic polyalcohol relative to 100 mass parts of representative examples of saturated aliphatic polyisocyanates in monomer group
Limit can exemplify 80 mass parts, 70 mass parts, 60 mass parts, 50 mass parts, 40 mass parts, 35 mass parts etc., and lower limit can illustrate
75 mass parts, 70 mass parts, 60 mass parts, 50 mass parts, 40 mass parts, 30 mass parts etc. out.In 1 embodiment, phase
For 100 mass parts of representative examples of saturated aliphatic polyisocyanates, the content of representative examples of saturated aliphatic polyalcohol is preferably 30 mass parts~80 matter
Measure part.
In content of the representative examples of saturated aliphatic polyalcohol relative to 100 moles of % of representative examples of saturated aliphatic polyisocyanates in monomer group
Limit can exemplify 80 moles of %, 70 moles of %, 60 moles of %, 50 moles of %, 40 moles of %, 35 moles of % etc., and lower limit can illustrate
75 moles of %, 70 moles of %, 60 moles of %, 50 moles of %, 40 moles of %, 30 moles of % etc. out.In 1 embodiment, phase
For 100 moles of % of representative examples of saturated aliphatic polyisocyanates, the content of representative examples of saturated aliphatic polyalcohol is preferably 30~80 moles of %.
<polyether polyol>
In the application, " polyether polyol " refers to the repetition list comprising ehter bond with 2 or more hydroxyls and 2 or more
The compound of member.Polyether polyol can be applied in combination two or more.In 1 embodiment, polyether polyol structural formula
C1 is indicated.
HO-(R3’-O-)nH (structural formula C1)
(in formula, R3’For alkylidene or cycloalkylidene, the integer that n is 2 or more.)
Polyether polyol can exemplify polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc..
The upper limit of the weight average molecular weight (Mw) of polyether polyol can exemplify 100,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,
5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..In 1 embodiment party
In formula, the weight average molecular weight (Mw) of polyether polyol is preferably 1000~100,000.
The upper limit of the number-average molecular weight (Mn) of polyether polyol can exemplify 100,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,
5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..In 1 embodiment party
In formula, the number-average molecular weight (Mn) of polyether polyol is preferably 1000~100,000.
Weight average molecular weight and number-average molecular weight can be by using gel permeation chromatograph (such as TOSOH Co., Ltd's systems, quotient
The name of an article " HLC-8220 ", chromatographic column: TOSOH Co., Ltd's system, method of trade name " TSK gel super HZ-M " etc. are surveyed
Fixed (same as below).
<polyester polyol>
In the application, " polyester polyol " refer to 2 or more hydroxyls and 2 or more in the molecule comprising ester bond
Repetitive unit compound.Polyester polyol can be applied in combination two or more.In 1 embodiment, polyester polyol
It is indicated with structural formula C2.
HO-{R4a’-OC(O)-R4b’-C(O)O}m-R4a’- OH (structural formula C2)
(in formula, R4a’And R4b’It is each independently alkylidene or cycloalkylidene, the integer that m is 2 or more.)
The usual pure and mild polyester polyol of polyether polyols separately includes multiple ehter bonds for belonging to hydrophily key, ester bond, therefore, benefit
The protective film quilt manufactured with carbamate (methyl) acrylate for using polyether polyol and/or polyester polyol to manufacture
Think that moisture readily penetrates through protective film (moisture permeability is high), it is found that the low film of moisture permeability can be manufactured.
In the application, " polyester polyol " is the reaction product of polycarboxylic acids or its acid anhydrides and polyalcohol.
Polycarboxylic acids can exemplify dicarboxylic acids etc..
Dicarboxylic acids can exemplify ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, nonyl two
Acid, decanedioic acid, dodecanedioic acid, 2- methylsuccinic acid, 2- methyl adipic acid, 3- methyl adipic acid, 3- methylglutaric acid, 2- first
Base suberic acid, 3,8- dimethyl decanedioic acid, 3,7- dimethyl decanedioic acid, phthalic acid, terephthalic acid (TPA), M-phthalic acid,
Dicarboxylic acids such as naphthalenedicarboxylic acid, trimellitic acid, trimesic acid, cyclohexane cyclohexanedimethanodibasic etc..
Polycarboxylic acid anhydride can exemplify acetic anhydride, propionic andydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic acid
Acid anhydride etc..
Polyalcohol can exemplify above-mentioned alkylidene polyol, above-mentioned cycloalkylidene polyalcohol etc..
The upper limit of the weight average molecular weight (Mw) of polyester polyol can exemplify 100,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,
5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..In 1 embodiment party
In formula, the weight average molecular weight (Mw) of polyester polyol is preferably 1000~100,000.
The upper limit of the number-average molecular weight (Mn) of polyester polyol can exemplify 100,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,
5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..In 1 embodiment party
In formula, the number-average molecular weight (Mn) of polyester polyol is preferably 1000~100,000.
Relative to 100 mass parts of monomer group, the upper content limit of polyether polyol and/or polyester polyol can exemplify 10 matter
Measure part, 9 mass parts, 8 mass parts, 7 mass parts, 6 mass parts, 5 mass parts, 4 mass parts, 3 mass parts, 2 mass parts, 1 mass parts,
0.5 mass parts etc., lower limit can exemplify 10 mass parts, 9 mass parts, 8 mass parts, 7 mass parts, 6 mass parts, 5 mass parts, 4 matter
Measure part, 3 mass parts, 2 mass parts, 1 mass parts, 0.5 mass parts, 0.2 mass parts etc..In 1 embodiment, from low-moisture permeability
From the perspective of, relative to 100 mass parts of monomer group, the content of polyether polyol and/or polyester polyol is preferably 0.2~10
Mass parts.
Relative to 100 moles of % of monomer group, the upper content limit of polyether polyol and/or polyester polyol can exemplify 1 and rub
Your %, 0.75 mole of %, 0.5 mole of %, 0.25 mole of %, 0.1 mole of %, 0.05 mole of % etc., lower limit can exemplify 0.9 and rub
Your %, 0.75 mole of %, 0.5 mole of %, 0.25 mole of %, 0.1 mole of %, 0.05 mole of %, 0.02 mole of % etc..At 1
In embodiment, relative to 100 moles of % of monomer group, the content of polyether polyol and/or polyester polyol is preferably 0.02 to rub
You are %~1 mole %.
Polyether polyol and/or polyester polyol in monomer group is relative to 100 mass of representative examples of saturated aliphatic polyisocyanates
The upper content limit of part can exemplify 20 mass parts, 15 mass parts, 10 mass parts, 5 mass parts, 1 mass parts, 0.5 mass parts etc., under
Limit can exemplify 19 mass parts, 15 mass parts, 10 mass parts, 5 mass parts, 1 mass parts, 0.5 mass parts, 0.4 mass parts etc..?
In 1 embodiment, relative to 100 mass parts of representative examples of saturated aliphatic polyisocyanates, polyether polyol and/or polyester polyol
Content is preferably 0.4 mass parts~20 mass parts.
Polyether polyol and/or polyester polyol in monomer group are rubbed relative to representative examples of saturated aliphatic polyisocyanates 100
The upper content limit of your % can exemplify 2 moles of %, 1 mole of %, 0.5 mole of %, 0.1 mole of % etc., and lower limit can exemplify 1.9 and rub
Your %, 1 mole of %, 0.5 mole of %, 0.1 mole of %, 0.04 mole of % etc..In 1 embodiment, relative to saturated fat
The content of 100 moles of % of race's polyisocyanates, polyether polyol and/or polyester polyol is preferably that 0.04 mole of %~2 is rubbed
You are %.
Polyether polyol and/or polyester polyol in monomer group is relative to 100 mass parts of representative examples of saturated aliphatic polyalcohol
Upper content limit can exemplify 100 mass parts, 90 mass parts, 75 mass parts, 50 mass parts, 25 mass parts, 10 mass parts, 5 mass
Part, 1 mass parts, 0.9 mass parts etc., lower limit can exemplify 90 mass parts, 75 mass parts, 50 mass parts, 25 mass parts, 10 mass
Part, 5 mass parts, 1 mass parts, 0.9 mass parts, 0.5 mass parts etc..It is polynary relative to representative examples of saturated aliphatic in 1 embodiment
The content of 100 mass parts of alcohol, polyether polyol and/or polyester polyol is preferably 0.5~100 mass parts.
Polyether polyol and/or polyester polyol in monomer group is relative to 100 moles of %'s of representative examples of saturated aliphatic polyalcohol
Upper content limit can exemplify 10 moles of %, 9 moles of %, 7.5 moles of %, 5 moles of %, 2.5 moles of %, 1 mole of %, 0.5 are rubbed
Your %, 0.1 mole of %, 0.09 mole of % etc., lower limit can exemplify 9 moles of %, 7.5 moles of %, 5 moles of %, 2.5 moles of %, 1
Mole %, 0.5 mole of %, 0.1 mole of %, 0.09 mole of %, 0.05 mole of % etc..In 1 embodiment, relative to saturation
The content of 100 mass parts of aliphatic polyol, polyether polyol and/or polyester polyol is preferably 0.05~10 mole of %.
<(methyl) acrylate of hydroxyl>
In the application, " (methyl) acrylate of hydroxyl " refers to the change with hydroxyl He (methyl) acrylate position
Close object.(methyl) acrylate of hydroxyl can be applied in combination two or more.In 1 embodiment, (the first of hydroxyl
Base) acrylate indicates with structural formula D.
[chemical formula 7]
(in formula, R5a’For alkylidene or cycloalkylidene, R5b’For hydrogen atom or methyl.)
(methyl) acrylate of hydroxyl can exemplify (methyl) propenoic acid beta-hydroxy base ethyl ester, (methyl) propenoic acid beta-hydroxy
Base propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl,
Modified (methyl) propenoic acid beta-hydroxy base ethyl ester of (methyl) acrylic acid 8- hydroxyl monooctyl ester, 6-caprolactone etc. has containing for 1 esteratic site
(methyl) acrylate of hydroxyl；Pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate etc. have multiple esteratic sites
(methyl) acrylate of hydroxyl etc..
Relative to 100 mass parts of monomer group, the upper content limit of (methyl) acrylate of hydroxyl can exemplify 60 mass
Part, 50 mass parts, 40 mass parts, 30 mass parts, 20 mass parts, 10 mass parts etc., lower limit can exemplify 55 mass parts, 50 mass
Part, 40 mass parts, 30 mass parts, 20 mass parts, 10 mass parts, 8 mass parts etc..In 1 embodiment, relative to monomer group
100 mass parts, the content of (methyl) acrylate of hydroxyl are preferably 8 mass parts~60 mass parts.
Relative to 100 moles of % of monomer group, the upper content limit of (methyl) acrylate of hydroxyl can exemplify 40 and rub
Your %, 30 moles of %, 20 moles of % etc., lower limit can exemplify 35 moles of %, 30 moles of %, 20 moles of %, 15 moles of % etc..?
In 1 embodiment, relative to 100 moles of % of monomer group, the content of (methyl) acrylate of hydroxyl is preferably 15 to rub
You are %~40 mole %.
(methyl) acrylate of hydroxyl in monomer group is relative to 100 mass parts of representative examples of saturated aliphatic polyisocyanates
Upper content limit can exemplify 240 mass parts, 200 mass parts, 150 mass parts, 100 mass parts, 50 mass parts, 25 mass parts etc.,
Lower limit can exemplify 230 mass parts, 200 mass parts, 150 mass parts, 100 mass parts, 50 mass parts, 25 mass parts, 18 mass
Part etc..In 1 embodiment, relative to 100 mass parts of representative examples of saturated aliphatic polyisocyanates, (methyl) acrylic acid of hydroxyl
The content of ester is preferably 18~240 mass parts.
(methyl) acrylate of hydroxyl in monomer group is relative to 100 moles of %'s of representative examples of saturated aliphatic polyisocyanates
Upper content limit can exemplify 100 moles of %, 75 moles of %, 50 moles of %, 40 moles of % etc., lower limit can exemplify 90 moles of %,
75 moles of %, 50 moles of %, 40 moles of %, 30 moles of % etc..In 1 embodiment, relative to representative examples of saturated aliphatic polyisocyanate cyanogen
100 moles of % of acid esters, the content of (methyl) acrylate of hydroxyl are preferably 30~100 moles of %.
Content of (methyl) acrylate of hydroxyl in monomer group relative to 100 mass parts of representative examples of saturated aliphatic polyalcohol
The upper limit can exemplify 500 mass parts, 400 mass parts, 300 mass parts, 200 mass parts, 150 mass parts, 100 mass parts, 50 matter
Part, 25 mass parts etc. are measured, lower limit can exemplify 400 mass parts, 300 mass parts, 200 mass parts, 150 mass parts, 100 mass
Part, 50 mass parts, 25 mass parts, 15 mass parts etc..In 1 embodiment, relative to 100 mass of representative examples of saturated aliphatic polyalcohol
Part, the content of (methyl) acrylate of hydroxyl is preferably 15 mass parts~500 mass parts.
Content of (methyl) acrylate of hydroxyl in monomer group relative to 100 moles of % of representative examples of saturated aliphatic polyalcohol
The upper limit can exemplify 300 moles of %, 200 moles of %, 150 moles of %, 100 moles of %, 50 moles of % etc., and lower limit can exemplify
200 moles of %, 150 moles of %, 100 moles of %, 50 moles of %, 25 moles of % etc..In 1 embodiment, relative to saturation
100 moles of % of aliphatic polyol, the content of (methyl) acrylate of hydroxyl are preferably 25~300 moles of %.
(methyl) acrylate of hydroxyl in monomer group is relative to 100 matter of polyether polyol and/or polyester polyol
The upper content limit of amount part can exemplify 125 mass parts, 100 mass parts, 90 mass parts, 75 mass parts, 50 mass parts, 25 mass
Part, 10 mass parts, 5 mass parts, 1 mass parts, 0.9 mass parts, 0.5 mass parts etc., lower limit can exemplify 100 mass parts, 90 matter
Measure part, 75 mass parts, 50 mass parts, 25 mass parts, 10 mass parts, 5 mass parts, 1 mass parts, 0.9 mass parts, 0.5 mass parts,
0.3 mass parts etc..In 1 embodiment, relative to 100 mass of polyether polyol and/or polyester polyol in monomer group
Part, the content of (methyl) acrylate of hydroxyl is preferably 0.3~125 mass parts.
(methyl) acrylate of hydroxyl in monomer group rubs relative to polyether polyol and/or polyester polyol 100
The upper content limit of your % can exemplify 7 moles of %, 5 moles of %, 4 moles of %, 2 moles of %, 1 mole of %, 0.9 mole of %, 0.5 are rubbed
Your %, 0.1 mole of %, 0.09 mole of % etc., lower limit can exemplify 5 moles of %, 4 moles of %, 2 moles of %, 1 mole of %, 0.9 are rubbed
Your %, 0.5 mole of %, 0.1 mole of %, 0.09 mole of %, 0.05 mole of % etc..In 1 embodiment, containing in monomer group
(methyl) acrylate of hydroxyl is preferably 0.05 relative to the content of 100 moles of % of polyether polyol and/or polyester polyol
~7 moles of %.
<other monomers>
Carbamate (methyl) acrylate, which also can be used, is not belonging to representative examples of saturated aliphatic polyisocyanates, saturated fat
Race's polyalcohol, polyether polyol, polyester polyol, hydroxyl any one of (methyl) acrylate monomer (below
Referred to as " other monomers ").Other monomers can exemplify acryloyl morpholine, isobornyl acrylate, dicyclopentanyl acrylate etc.
Monofunctional acrylate/polyfunctional acrylic ester without hydroxyl etc..
Other monomers can exemplify 5 mass parts, 4 mass parts relative to the content of 100 mass parts of monomer group, lower than 1 mass
Part, 0 mass parts etc..
Other monomers can exemplify 5 moles of %, 4 moles of % relative to the content of 100 moles of % of monomer group, rub lower than 1
Your %, 0 mole of % etc..
<physical property etc. of carbamate (methyl) acrylate>
The upper limit of the weight average molecular weight (Mw) of carbamate (methyl) acrylate can exemplify 100,000,7.5 ten thousand, 50,000,
2.5 ten thousand, 10,000,5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..?
In 1 embodiment, the weight average molecular weight (Mw) of carbamate (methyl) acrylate is preferably 1000~100,000.
The upper limit of the number-average molecular weight (Mn) of carbamate (methyl) acrylate can exemplify 100,000,7.5 ten thousand, 50,000,
2.5 ten thousand, 10,000,5000,2000 etc., lower limit can exemplify 90,000,7.5 ten thousand, 50,000,2.5 ten thousand, 10,000,5000,2000,1000 etc..?
In 1 embodiment, the number-average molecular weight (Mn) of carbamate (methyl) acrylate is preferably 1000~100,000.
Relative to 100 mass parts of carbamate (methyl) acrylate, the upper limit of the containing ratio of cycloalkylidene can be illustrated
48 mass parts, 45 mass parts, 40 mass parts, 35 mass parts, 30 mass parts, 25 mass parts, 20 mass parts etc. out, lower limit can illustrate
45 mass parts, 40 mass parts, 35 mass parts, 30 mass parts, 25 mass parts, 20 mass parts, 19 mass parts etc. out.Implement at 1
In mode, relative to 100 mass parts of carbamate (methyl) acrylate, the cycloalkylidene comprising 19~48 mass parts.This
In application, " relative to 100 mass parts of carbamate (methyl) acrylate, the cycloalkylidene comprising A mass parts " refer to: example
1,4-CHDM is such as used only as the monomer with cycloalkylidene to manufacture carbamate (methyl) acrylate
In the case where, relative to 100 mass parts of molecular weight (formula weight) of carbamate (methyl) acrylate, the formula weight of cyclohexylene
For A mass parts.
As manufacture carbamate (methyl) acrylate method, as long as make representative examples of saturated aliphatic polyisocyanates,
(methyl) acrylate of representative examples of saturated aliphatic polyalcohol, polyether polyol and/or polyester polyol and hydroxyl reacts
Method, there is no particular limitation, well known manufacturing method can be exemplified.Above-mentioned manufacturing method can exemplify: by saturated fat
(methyl) third of race's polyisocyanates, representative examples of saturated aliphatic polyalcohol, polyether polyol and/or polyester polyol and hydroxyl
The method that olefin(e) acid ester is mixed to manufacture；By representative examples of saturated aliphatic polyisocyanates, representative examples of saturated aliphatic polyalcohol, polyether polyol
And/or after polyester polyol mixes together and reacts it, (methyl) acrylate of itself and hydroxyl is made to react to make
The method etc. made.
From the viewpoint of toxicity and low-moisture permeability, the total material amount of hydroxyl possessed by each monomer in monomer group with it is different
The molar ratio (OH/NCO) of the total material amount of cyanic acid ester group is preferably 1.0~1.1.
[actinic energy ray curable resion composition]
The application provides the active energy ray-curable resin group comprising above-mentioned carbamate (methyl) acrylate
Close object.Above-mentioned composition can compatibly use in coating applications.
The upper content limit of above-mentioned carbamate (methyl) acrylate in composition can exemplify 100 mass parts, 90
Mass parts, 80 mass parts, 70 mass parts, 60 mass parts, 55 mass parts etc., lower limit can exemplify 95 mass parts, 90 mass parts, 80
Mass parts, 70 mass parts, 60 mass parts, 55 mass parts, 50 mass parts etc..In 1 embodiment, from the viewpoint of low-moisture permeability
It sets out, relative to 100 mass parts of above-mentioned composition, preferably comprises the above-mentioned carbamate (first of 50 mass parts~100 mass parts
Base) acrylate.
In 1 embodiment, above-mentioned composition includes Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can be applied in combination two
Kind or more.Photoepolymerizationinitiater initiater can exemplify 1- hydroxy-cyclohexyl-phenyl ketone, 2,2- dimethoxy -1,2- diphenylethane -
1- ketone, 1- cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -
2- hydroxy-2-methyl-1- propane-1- ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propane-1- ketone, 2,4,6-
Trimethylbenzoy-dipheny-phosphine oxide, 4- methyl benzophenone etc..
In 1 embodiment, from the viewpoint of curability, the content of Photoepolymerizationinitiater initiater is relative to composition 100
Mass parts can exemplify 3.0 mass parts~7.0 mass parts etc., in other embodiments, relative to carbamate (methyl)
100 mass parts of acrylate can exemplify 3.0 mass parts~14 mass parts etc..
In 1 embodiment, above-mentioned composition includes retarder thinner.Retarder thinner can be applied in combination two or more.
Retarder thinner can exemplify methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, butyl acetate, ethyl alcohol, normal propyl alcohol, different
Propyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, diacetone alcohol, acetylacetone,2,4-pentanedione, toluene, dimethylbenzene, n-hexane, hexamethylene, methyl ring
Hexane, normal heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, Isosorbide-5-Nitrae-dioxanes, propylene glycol monomethyl ether, ethylene glycol list second
Base ether acetic acid ester, propylene glycol monomethyl ether etc..In 1 embodiment, from the viewpoint of viscosity when being suitable for coating
It sets out, the content of retarder thinner can exemplify 0 mass parts~400 mass parts or so etc. relative to 100 mass parts of composition.At it
In its embodiment, relative to 100 mass parts of carbamate (methyl) acrylate, 0 mass parts~800 mass can be exemplified
Part or so etc..
Above-mentioned composition may include in addition to carbamate (methyl) acrylate, Photoepolymerizationinitiater initiater, retarder thinner
Except preparation as additive.Additive can exemplify antioxidant, ultraviolet absorbing agent, light stabilizer, defoaming agent, surface
Regulator, antistain agent, inorganic filler, silane coupling agent, colloidal silicon dioxide, pigment, antistatic agent, metal oxide microparticle
Dispersion etc..In 1 embodiment, the content of additive can exemplify 5 mass parts, 4 matter relative to 100 mass parts of composition
Part is measured, is lower than 1 mass parts, is lower than 0.1 mass parts, lower than 0.01 mass parts, 0 mass parts etc., in other embodiments, relatively
In 100 mass parts of carbamate (methyl) acrylate, can exemplify 5 mass parts, 4 mass parts, lower than 1 mass parts, be lower than
0.1 mass parts, lower than 0.01 mass parts, 0 mass parts etc..
[solidfied material]
The application provides the solidfied material of above-mentioned actinic energy ray curable resion composition.Above-mentioned solidfied material can by pair
Above-mentioned actinic energy ray curable resion composition irradiates ultraviolet light, electron ray, radioactive ray isoreactivity energy-ray to obtain
?.
Ultraviolet light source can exemplify xenon lamp, high-pressure sodium lamp, metal halide lamp, LED light etc..Amount of ultraviolet can be according to solid
The thickness of compound is suitably adjusted.
[protective film]
The application provides the protective film including above-mentioned solidfied material.Said protection film is by the inclusion of being coated on substrate
Process, irradiation active energy beam solidify it and the method for process that is laminated manufactures.In addition, irradiation active energy beam
Process can carry out in the drying of coating material and/or after dry.
Substrate can exemplify polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polyphenyl
Ethylene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norborneol
Alkene system resin etc..
Coating method can exemplify bar coater coating, Meyer stick (Meyer Bar) coating, airblade coating, intaglio plate coating, anti-
To intaglio plate coating, hectographic printing, flexographic printing, silk screen print method etc..
Said protection film can be used for barrier film, polarization plates, film for packaging etc..
Embodiment
Hereinafter, enumerate synthesis example, embodiment and comparative example, the present invention is further illustrated, but the present invention is not limited to
These embodiments.It should be noted that in the following description, in case of no particular description, part and % are quality base
It is quasi-.
<synthesis example 1>(synthesis of the urethane acrylate comprising cycloalkylidene)
Hydrogenated xylene diisocyanate is put into the three-necked flask for being equipped with blender, thermometer, reflux condensation mode machine
(H-XDI) 31.6 parts, 16.0 parts of Tricyclodecane Dimethanol (hereinafter referred to as TCDDM), polyether polyol (trade name " Uniol D-
2000 ", Japan Oil Co's system) 3.5 parts, 30.0 parts of butyl acetate, tin octoate 0.01g, its reaction is made at 80 DEG C.It is remaining
Isocyanate group at the time of reach 8.4%, addition 18.9 parts of acrylic acid 2- hydroxy methacrylate (HEA), tin octoate 0.01g, to benzene
Diphenol monomethyl ether 0.07g reacts until remaining isocyanate group reaches 0.1% or less, and obtaining resin component is 70%
Urethane acrylate solution 100g (A-1).
Synthesis example other than synthesis example 1 and compare in synthesis example, in addition to changed as following table reacted constituent it
Outside, it is carried out similarly with synthesis example 1.
[table 1]
1A ' -6 is crystallized with the progress of reaction, can not be synthesized.
H-XDI: hydrogenated xylene diisocyanate
NBDI: norbornene diisocyanate
HDI: hexamethylene diisocyanate
TCDDM: Tricyclodecane Dimethanol
DEPD:2,4- diethyl -1,5-PD
CHDM:1,4- cyclohexanedimethanol
Polyether polyol (trade name " Uniol D-2000 ", Japan Oil Co's system)
Polyester polyol (trade name " Kuraray Polyol P-4010 ", Kuraray Co. Ltd. system)
HEA: acrylic acid 2- hydroxy methacrylate
PE3A: pentaerythritol triacrylate
Then, it is shown as the embodiment of the cured film of carbamate of the invention (methyl) acrylate.
Embodiment 1
By 54.4 parts of urethane acrylate (A-1), as the IRGACURE184 of Photoepolymerizationinitiater initiater
(Irg.184) 1.9 parts, 43.7 parts of methyl ethyl ketone (MEK) be stirred until homogeneous, it is solid to obtain the active energy beam that solid component is 40%
The property changed resin combination.
Embodiment 2~5, the Comparative Examples 1 to 5
Hereinafter, similarly carrying out the preparation of actinic energy ray curable resion composition according to the mixed ratio of table 2.
[table 2]
<production of desciccator diaphragm>
Using bar coater No20, by the active energy ray-curable resin group of above-described embodiment 1~5 and the Comparative Examples 1 to 5
Closing object hardened coating in such a way that dry film thickness reaches 10 μm makes it at 90 DEG C on tri acetyl cellulose membrane or on glass plate
It is 3 minutes dry.
<production of cured film>
Using 1 high-pressure sodium lamp with 80W, cumulative exposure 300mJ/cm2Mode be irradiated, by Examples 1 to 5
Cured film is made with the drying membrane stage of the Comparative Examples 1 to 5, and carries out following evaluations.
<evaluation of the moisture permeability of cured film>
Using the cured film made on tri acetyl cellulose membrane, according to the moisture permeability test method (agar diffusion method) of JIS Z 0208
It is measured.In 40 DEG C of temperature, the atmosphere of humidity 90%RH, measurement passes through every 1m of test film for 24 hours2The water of area steams
The grams of gas.
<evaluation of the breaking strength of cured film>
The single cured film obtained using the solidification film stripping that will be made on a glass, according to JIS K 7127 film and
The test method of the tensile properties of the experimental condition and JIS K 7161 of piece is measured.
By Examples 1 to 5 and the Comparative Examples 1 to 5 evaluation result is shown in table 3.
[table 3]
| Moisture permeability [g/m2·24h] | Breaking strength [MPas] | |
| Embodiment 1 | 55 | 102 |
| Embodiment 2 | 78 | 90 |
| Embodiment 3 | 60 | 104 |
| Embodiment 4 | 76 | 90 |
| Embodiment 5 | 69 | 105 |
| Comparative example 1 | 165 | 50 |
| Comparative example 2 | 95 | 65 |
| Comparative example 3 | 36 | It can not measure※ |
| Comparative example 4 | 52 | It can not measure※ |
| Comparative example 5 | 80 | 70 |
Because breaking strength is weak, test film is broken ※ in the assay.
Claims (5)
1. a kind of carbamate (methyl) acrylate is the reactant of monomer group, the monomer group includes:
Representative examples of saturated aliphatic polyisocyanates,
Representative examples of saturated aliphatic polyalcohol,
Polyether polyol and/or polyester polyol and
(methyl) acrylate of hydroxyl,
Relative to 100 mass parts of monomer group, include 0.2 mass parts~10 mass parts polyether polyol and/or institute
Polyester polyol is stated,
Relative to 100 mass parts of carbamate (methyl) acrylate, include 19 mass parts~48 mass parts cycloalkylidene.
2. carbamate (methyl) acrylate according to claim 1, it includes:
Following structure A from the representative examples of saturated aliphatic polyisocyanates,
-CO-NH-R1- NH-CO- (structure A)
In formula, R1For alkylidene or cycloalkylidene；
Following structure B from the representative examples of saturated aliphatic polyalcohol,
-O-R2- O- (structure B)
In formula, R2For alkylidene or cycloalkylidene；
Following structure Cs 1 from the polyether polyol and/or following structure Cs 2 from the polyester polyol,
In formula, R3For alkylidene or cycloalkylidene, the integer that n is 2 or more,
In formula, R4For alkylidene or cycloalkylidene, the integer that m is 2 or more；And
Following structure D of (methyl) acrylate from the hydroxyl,
-O-R5a-O-C(O)-CR5b=CH2(structure D)
In formula, R5aFor alkylidene or cycloalkylidene, R5bFor hydrogen or methyl.
3. a kind of actinic energy ray curable resion composition, it includes carbamate (first of any of claims 1 or 2
Base) acrylate.
4. a kind of solidfied material is the solidfied material of actinic energy ray curable resion composition as claimed in claim 3.
5. a kind of protective film, it includes solidfied materials as claimed in claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-120098 | 2017-06-20 | ||
| JP2017120098 | 2017-06-20 |
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| JP2020176161A (en) * | 2019-04-15 | 2020-10-29 | 旭化成株式会社 | Curable composition |
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| CN115057988A (en) * | 2022-06-21 | 2022-09-16 | 惠州市浩明科技股份有限公司 | Thermoplastic elastomer and protective film |
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| CN102933629A (en) * | 2011-01-13 | 2013-02-13 | Dic株式会社 | Radical-curable hot-melt urethane resin composition and moldings for optical use |
| CN105073806A (en) * | 2013-03-27 | 2015-11-18 | 第一工业制药株式会社 | Energy ray-curable resin composition |
| WO2017029280A1 (en) * | 2015-08-17 | 2017-02-23 | Basf Se | Aqueous polymer compositions comprising polyurethane (meth)acrylates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102933629A (en) * | 2011-01-13 | 2013-02-13 | Dic株式会社 | Radical-curable hot-melt urethane resin composition and moldings for optical use |
| CN105073806A (en) * | 2013-03-27 | 2015-11-18 | 第一工业制药株式会社 | Energy ray-curable resin composition |
| WO2017029280A1 (en) * | 2015-08-17 | 2017-02-23 | Basf Se | Aqueous polymer compositions comprising polyurethane (meth)acrylates |
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| Publication number | Publication date |
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| JP6874740B2 (en) | 2021-05-19 |
| JP2019006994A (en) | 2019-01-17 |
| KR102352868B1 (en) | 2022-01-17 |
| KR20180138190A (en) | 2018-12-28 |
| TWI767014B (en) | 2022-06-11 |
| CN109096469B (en) | 2021-11-09 |
| TW201905019A (en) | 2019-02-01 |
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