CN107075332A - Surface protection film adhesive composition and surface protection film - Google Patents
Surface protection film adhesive composition and surface protection film Download PDFInfo
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- CN107075332A CN107075332A CN201580058487.1A CN201580058487A CN107075332A CN 107075332 A CN107075332 A CN 107075332A CN 201580058487 A CN201580058487 A CN 201580058487A CN 107075332 A CN107075332 A CN 107075332A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
The surface protection film adhesive composition that the adhesive phase that the contaminative and metal protection reduced to clung body can be formed and there is the rise of the bonding force after appropriate bonding force and high temperature manufacturing process to be inhibited is provided and the surface protection film with described adhesive layer of the invention.The composition is the surface protection film adhesive composition containing (methyl) acrylic resin (A) and hexamethylene diisocyanate class crosslinking agent (B), wherein, (methyl) acrylic resin (A) is obtained by carrying out polymerisation in solution to the polymerizable monomer for containing (methyl) alkyl acrylate of alkyl carbon number below 4 with the amount in the range of 30.0~99 mass %, and with following (a1), (a2) and (a3) characteristic, the hexamethylene diisocyanate class crosslinking agent (B) is contained with amount of the gel fraction of the adhesive phase formed by the surface protection film with adhesive composition in the range of 90.0~99.9 mass %.(a1) weight average molecular weight (Mw) of the polystyrene conversion determined by gel permeation chromatography (GPC method) is in the range of 1,200,000~2,000,000, (a2) molecular weight distribution (Mw/Mn) is in the range of 4~9, and (a3) acid number is in below 2mg KOH/g.
Description
Technical field
The present invention relates to surface protection film adhesive composition and surface protection film.
Background technology
In recent years, the display device such as liquid crystal display device and plasma scope of smart mobile phone and tablet PC etc. is obtained
To widely using.If observing the section of this display device, it, which has, includes the slim multilayer laminate constructions of various functions,
Form the optics functional membrane more and more higher functionalization of these multilayer laminate constructions.In order to stably produce keeping by this
The display device constituted with H.D optics with functional membrane is, it is necessary to attach the surface damage for preventing display device
Surface protection film.
Surface protection film generally has membranaceous supporting mass and the adhesive phase formed on the face of its at least one party, by making
Adhesive phase part is contacted with clung body so that surface protection film is bonded in clung body.For surface protection film, it is desirable to attach in
There is sufficient bonding force, while the attachment of residue is lacked caused by described adhesive layer when peeling off during clung body.
In addition, as one of the optics functional membrane for display device, life is largely developed towards touch-screen
Tin indium oxide (ITO) film of production is more to be manufactured by high temperature manufacturing process.Therefore, for surface protection film and adhesive phase
The problem of peeling off bad caused by the rising for seeking the burn into bonding force for also not occurring metal oxide etc. after high-temperature technology.
As surface protection film adhesive, for example Patent Document 1 discloses by acrylic resin and crosslinking agent
The adhesive of formation.But, due to the low value that the gel fraction of adhesive is 0~30 mass %, exist it is easily contaminated and
The problem of bonding force after heat-resisting is raised.
Patent Document 2 discloses carry out acrylic resin obtained by copolymerization to the monomer containing the monomer with carboxyl
With adhesive obtained by crosslinking agent blending.But, the Weight-average molecular of the acrylic resin disclosed in the embodiment of patent document 2
Measure as 600,000, be not sufficiently high molecular weight, stain resistance is insufficient.In addition, the usage amount of the monomer with carboxyl with
The higher value for being 5~10 mass % in the mass % of polymerizable monomer 100 for forming acrylic resin, therefore be attached at
During clung body comprising metal oxide etc., exist clung body be corroded so that it is heat-resisting after bonding force the problem of rise.
Patent Document 3 discloses to specific (methyl) alkyl acrylate and include the monomer of the monomer with carboxyl
Carry out acrylic resin obtained by copolymerization and the adhesive of epoxy crosslinking agent formation.But, exist by acrylic resin
Acid number caused by 16~120mg KOH/g high level the corrosion of the clung body comprising metal oxide etc. and it is heat-resisting after it is viscous
The problem of raising with joint efforts, and due to caused using epoxy crosslinking agent the pliability of adhesive phase it is insufficient, to clung body
Wetability it is poor the problem of.
Prior art literature
Patent document
Patent document 1:Japanese Patent Laid-Open 2009-79074 publications
Patent document 2:Japanese Patent Laid-Open 2007-126606 publications
Patent document 3:International Publication No. 2011/148721
The content of the invention
The technical problems to be solved by the invention
The technical problem of the present invention is that offer can form reduction to such as hardcoat film and antireflection film, ITO
The optics of film is with the contaminative and metal protection of the clung body that functional membrane is representative and with appropriate bonding force and high temperature
The surface protection film adhesive composition for the adhesive phase that the rise of bonding force after manufacturing process is inhibited and have
The surface protection film of described adhesive layer.
Solve the technical scheme that technical problem is used
The surface protection film of the present invention is containing (methyl) acrylic resin (A) and hexa-methylene with adhesive composition
The surface protection film adhesive composition of diisocyanates crosslinking agent (B), wherein,
(methyl) acrylic resin (A) passes through to containing alkyl with the amount in the range of 30.0~99.9 mass %
The polymerizable monomer of (methyl) alkyl acrylate of carbon number below 4 carries out polymerisation in solution and obtain, and have following (a1),
(a2) and (a3) characteristic,
With the gel fraction of adhesive phase that is formed by the surface protection film with adhesive composition 90.0~99.9
Amount in the range of quality % contains the hexamethylene diisocyanate class crosslinking agent (B).
(a1) weight average molecular weight (Mw) of the polystyrene conversion determined by gel permeation chromatography (GPC method) is 1,200,000
In the range of~200 ten thousand,
(a2) molecular weight distribution (Mw/Mn) is in the range of 4~9,
(a3) acid number is in below 2mg KOH/g.
In the surface protection film adhesive composition of the present invention, relative to (methyl) acrylic resin (A) 100
Mass parts, the content of the hexamethylene diisocyanate class crosslinking agent (B) is preferably in the range of 2~15 mass parts.
In addition, the surface protection film of the present invention is with membranaceous supporting mass and at least the one of the membranaceous supporting mass
The surface protection film of the adhesive phase formed on the face of side, wherein,
Described adhesive layer is formed by surface protection film with adhesive composition, and the surface protection film is combined with adhesive
Thing contains (methyl) acrylic resin (A) and hexamethylene diisocyanate class crosslinking agent (B),
(methyl) acrylic resin (A) passes through to containing alkyl with the amount in the range of 30.0~99.9 mass %
The polymerizable monomer of (methyl) alkyl acrylate of carbon number below 4 carries out polymerisation in solution and obtain, and have above-mentioned (a1),
(a2) and (a3) characteristic,
With the gel fraction of adhesive phase that is formed by the surface protection film with adhesive composition 90.0~99.9
Amount in the range of quality % contains the hexamethylene diisocyanate class crosslinking agent (B).
The surface protection film adhesive composition of the present invention passes through comprising to containing specifically (methyl) third with specified quantitative
The polymerizable monomer of olefin(e) acid ester carries out (methyl) acrylic resin obtained by polymerisation in solution and specific crosslinking agent, in energy
While sufficient bonding force enough is presented, it can be formed and not pollute clung body and then the viscous of metal erosion does not occur for clung body yet
Close layer.
Invention effect
Sufficient bonding force can be played when being attached at clung body, is dropped simultaneously by means of the invention it is possible to provide and may be formed at
Low contaminative and metal protection to clung body and then suppress the rising of the bonding force after high temperature manufacturing process and make by bonding
The surface protection film adhesive composition of the few adhesive phase of attachment of residue and with the bonding caused by oxidant layer
The surface protection film of oxidant layer.
Embodiment
Below, the surface protection film of the present invention is illustrated with adhesive composition and surface protection film.Hereinafter,
The surface protection film of the present invention is referred to as " adhesive composition " with adhesive composition.
Also acrylic acid and methacrylic acid are referred to as " (methyl) acrylic acid " in the present invention.
(surface protection film adhesive composition)
The surface protection film adhesive composition of the present invention contains (methyl) acrylic resin (A) and hexa-methylene two
Isocyanates crosslinking agent (B) (is also denoted as " HDI classes crosslinking agent (B) ") below, meanwhile, the adhesive composition has been usually contained
Machine solvent (C).
[(methyl) acrylic resin (A)]
(methyl) acrylic resin (A) is the poly- of (methyl) alkyl acrylate (i) below 4 containing alkyl carbon number
The polymer of conjunction property monomer, the polymer is obtained by carrying out polymerisation in solution to the polymerizable monomer in organic solvent.By
This, (methyl) acrylic resin (A) has the construction unit from (i).
As the polymerizable monomer, in addition to (methyl) alkyl acrylate (i) of alkyl carbon number below 4,
Can contain selected from (methyl) acrylate (ii), the monomer (iii) containing acidic group, other polar functionalities monomers (iv) and other
At least one of monomer (v).For example, can enumerate containing (i) and (iv), contain (ii), (iii) or (v) as needed
Polymerizable monomer.
Hereinafter, also (methyl) alkyl acrylate (i) by described in is designated as " monomer (i) ", by (methyl) acrylate (ii)
" monomer (ii) " is designated as, acid-based monomers (iii) will be contained and be designated as " monomer (iii) ", other polar functionalities monomers (iv) are remembered
It is designated as " monomer (v) " for " monomer (iv) ", other monomers (v).
《(methyl) alkyl acrylate (i) of alkyl carbon number below 4》
Monomer (i) is for example represented with following formula (i-1).
CH2=CR1-COOR2…(i-1)
R1It is hydrogen atom or methyl, R2It is alkyl of the carbon number below 4.
R2Alkyl be appointing in methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group and sec-butyl
It is a kind of.
As monomer (i), for example, it can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid
N-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid
The tert-butyl ester and (methyl) sec-butyl acrylate.
Monomer (i) can be used alone a kind, it is possible to use two or more.
In the mass % of polymerizable monomer 100 for forming (methyl) acrylic resin (A), the usage amount of monomer (i) is
30.0~99.9 mass %, preferably 33.0~99.9 mass %, more preferably 50.0~99.5 mass %, more preferably
50.0~99.0 mass %, particularly preferably 50.0~98.0 mass %.
If the usage amount of monomer (i) is within the above range, by the adhesive containing (methyl) acrylic resin (A)
The adhesive phase of composition formation has sufficient bonding force to clung bodies such as optics functional membranes, can suppress in conveying
Peel off or tilt.
《(methyl) acrylate (ii)》
Monomer (ii) is for example represented with following formula (ii-1).
CH2=CR3-COOR4…(ii-1)
R3For hydrogen atom or methyl.R4The group beyond alkyl of the carbon number below 4, and be without hydroxyl, amino,
The organic group of amide groups, cyano group and carboxyl isopolarity group.
It is used as R4, can enumerate the ester ring type such as alkyl, cycloalkyl of carbon number more than 5 base, aryl, aralkyl, with ehter bond
Organic group etc..Alkyl carbon number is usually 5~24.Cycloalkyl carbon number is usually 5~15.Aryl carbon number is usually 6~10.Aralkyl
Base is generally made up of the alkylidene of carbon number 1~6 and the aryl of carbon number 6~10., can example citing as the organic group with ehter bond
Group as shown in following formula (g-1).
-(R5O)nR6…(g-1)
Herein, R5It is alkylidene, R6It is alkyl or aryl, n is more than 1 integer.The carbon number of alkylidene is usually 1~10,
Preferably 1~5.The carbon number of alkyl is usually 1~10, and preferably 1~4, the carbon number of aryl is usually 6~10, and preferably 6.N is excellent
Elect 1~20, more preferably 1~4, more preferably 1~2 as.
As monomer (ii), (methyl) alkyl acrylate, (methyl) of the alkyl for example with carbon number more than 5 can be enumerated
(methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid of the groups containing ester ring type such as acrylate base ester
Aralkyl ester, (methyl) alkyl acrylate epoxide alkyl ester, many alkylene glycols ester (Japaneses of single (methyl) alkyl acrylate epoxide：アルコ
キ シ Port リ ア Le キ レ Application グ リ Us ー Le モ ノ (メ タ) ア Network リ レ ー ト) and (methyl) acrylic acid aryloxy group alkyl base ester.
, can example citing as (methyl) alkyl acrylate of the workable alkyl with carbon number more than 5 in the present invention
Such as (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, the positive heptyl ester of (methyl) acrylic acid, (methyl) acrylic acid 2- ethyls
Own ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid are different
Nonyl ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, methacrylic acid
Dodecyl ester, (methyl) octadecyl acrylate and (methyl) acrylic acid isooctadecane base ester.
In addition, being used as (methyl) acrylate, (methyl) third of the groups containing ester ring type such as (methyl) acrylate base ester
Olefin(e) acid aryl ester and (methyl) acrylic acid aralkyl ester, can enumerate such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid different
Norbornene ester, (methyl) phenyl acrylate and (methyl) benzyl acrylate.
Further, as (methyl) alkyl acrylate epoxide alkyl ester, can enumerate such as (methyl) methoxyethyl methyl esters,
(methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 3- methoxyl groups propyl ester,
(methyl) acrylic acid 3- ethyoxyls propyl ester, (methyl) acrylic acid 4- methoxybutyls, (methyl) acrylic acid 4- Ethoxybutyls.
As many alkylene glycols esters of list (methyl) alkyl acrylate epoxide, for example single (methyl) methoxyethyl two can be enumerated
Glycol ester, list (methyl) methoxyethyl DPG ester, single (methyl) ethioxy triglycol ester, single (first
Base) ethioxy binaryglycol ester, singly (methyl) methoxyethyl triglycol ester.
As (methyl) acrylic acid aryloxy group alkyl base ester, such as (methyl) acrylic acid phenoxy group methyl esters, (methyl) can be enumerated
Acrylic acid 2- phenoxy ethyls, (methyl) acrylic acid 2- toloxyls ethyl ester, (methyl) acrylic acid xylyloxy methyl esters, (first
Base) acrylic acid naphthoxy methyl esters.
Monomer (ii) can be used alone a kind, it is possible to use two or more.
In the mass % of polymerizable monomer 100 for forming (methyl) acrylic resin (A), the usage amount of monomer (ii) is preferred
For 0~69.9 mass %, more preferably more preferably 0~66.9 mass %, 0~49.5 mass %.
《Monomer (iii) containing acidic group》
As the acidic group contained by monomer (iii), such as carboxyl, anhydride group, phosphate, sulfate can be enumerated.
As the workable monomer containing carboxyl in the present invention, such as (methyl) propenoic acid beta-carboxyl second can be enumerated
Ester, (methyl) acrylic acid 5- carboxyls pentyl ester, succinic acid list (methyl) acrylyl oxy-ethyl ester and ω-carboxy-polycaprolactone list
(methyl) acrylate (Japanese：ω-カ Le ボ キ シ Port リ カ プ ロ ラ Network ト Application モ ノ (メ タ) ア Network リ レ ー ト) etc. contain
(methyl) acrylate of carboxyl；(methyl) acrylic acid；Butenoic acid；Maleic acid；Fumaric acid；Itaconic acid；Citraconic acid.
As the monomer containing anhydride group, such as maleic anhydride and itaconic anhydride can be enumerated., can example as phosphorous acid-based monomers
(methyl) acrylate on side chain with phosphate is lifted, as sulfur-bearing acid-based monomers, can enumerate has sulfuric acid on side chain
(methyl) acrylate of base.
Monomer (iii) can be used alone a kind, it is possible to use two or more.
In the mass % of polymerizable monomer 100 for forming (methyl) acrylic resin (A), the usage amount of monomer (iii) is excellent
Elect 0~0.3 mass %, particularly preferably more preferably 0~0.2 mass %, 0 mass % as.In the present invention, contained by adjusting this
The usage amount of the monomer (iii) of acidic group, can control the acid number of (methyl) acrylic resin (A).That is, monomer (iii) makes
If consumption is within the above range, the acid number of (methyl) acrylic resin (A) can be reduced.Acid number is lower, such as in quilt
Corrosion can be reduced when in viscous body using metal oxides such as ito films, so as to suppress the hard coat containing ito film and prevent
The performance reduction in reflecting layer etc..In addition, the bonding force rise after heat treatment can be suppressed.
When the usage amount of monomer (iii) is 0 mass %, in order to be imported in (methyl) acrylic resin (A) and six Asias
The crosslinking points of methyl diisocyanate class crosslinking agent (B), expect using having imported and hexamethylene diisocyanate class crosslinking agent
(B) NCO has the monomer (iv) being exemplified below of the group of reactivity.Use the situation of monomer (iii) and (iv)
Under, need to adjust the usage amount of monomer (iii) and (iv) certainly, so that crosslinking points and monomer (iv) that monomer (iii) is provided
The crosslinking points provided do not damage the characteristic of the surface protection film adhesive composition of the present invention.
《The monomer (iv) of other polar functionalities》
As monomer (iv), such as monomer containing hydroxyl, the monomer containing amino, the list containing amide groups can be enumerated
Body, the monomer containing nitrogen system heterocycle and the monomer containing cyano group.But, except the monomer containing acidic group.
As the monomer containing hydroxyl, (methyl) acrylate for example containing hydroxyl can be enumerated, (first can be specifically enumerated
Base) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (methyl) propylene
(methyl) hydroxyalkyl acrylates such as the sour own ester of 6- hydroxyls and (methyl) acrylic acid 8- hydroxyl monooctyl esters.(methyl) hydroxyalkyl acrylate
The carbon number of middle hydroxyalkyl is usually 1~12, and preferably 1~8.
As the monomer containing amino, such as (methyl) acrylate, (methyl) acrylic acid can be enumerated
(methyl) acrylate containing amino such as diethylamino ethyl ester.
As the monomer containing amide groups, such as (methyl) acrylamide, N- methyl (methyl) acrylamide, N- can be enumerated
Ethyl (methyl) acrylamide, N- propyl group (methyl) acrylamide, N- hexyls (methyl) acrylamide and N, N- dimethyl (first
Base) acrylamide.
As the monomer of nitrogenous system's heterocycle, such as vinyl pyrrolidone, acryloyl morpholine and vinyl can be enumerated in oneself
Acid amides.As the monomer containing cyano group, such as cyano group (methyl) acrylate and (methyl) acrylonitrile can be enumerated.
From also can be single from the point of view of the crosslinking points as (methyl) acrylic resin (A) and HDI classes crosslinking agent (B)
Body (iv) preferably comprises the monomer of hydroxyl.By using containing the monomer of hydroxyl as monomer (iv), it is assumed that (methyl) acrylic acid
The acid number of resinoid (A) is 0mg KOH/g, by containing hydroxyl that the monomer of hydroxyl brought as the isocyanic acid of hexa-methylene two
The crosslinking points of esters crosslinking agent (B), can also reduce rotten to the contaminative and metal of the optics functional membrane as clung body
Corrosion simultaneously realizes appropriate bonding force.
In the mass % of polymerizable monomer 100 for forming (methyl) acrylic resin (A), the usage amount of monomer (iv) is preferred
For 0.1~10 mass %, more preferably more preferably 1~8 mass %, 2~8 mass %.The usage amount of monomer (iv) is such as
Fruit is then able to ensure that the crosslinking points with hexamethylene diisocyanate class crosslinking agent (B), monomer (iv) more than the lower limit
If usage amount below the higher limit, can suppress the viscosity of (methyl) acrylic resin (A) becomes too high, can
Obtain good coating.
Especially, if the usage amount of the monomer containing hydroxyl is more than the lower limit, even if in monomer (iii)
In the case that usage amount is 0~0.3 mass %, 0~0.2 mass % or 0 mass %, cross-linked structure is also effectively formed, can
Obtain the adhesive phase with suitable cohesiveness.
Monomer (iv) can be used alone a kind, it is possible to use two or more.
《Other monomers (v)》
As other monomers (v), the vinyl esters such as vinyl acetate and propionate can be enumerated；Ethlyene dichloride and
The halogenated alkenes hydro carbons such as vinylidene chloride；The styrene monomer such as styrene and α-methylstyrene；Butadiene, isoprene and neoprene
The diene-based monomers such as diene.
Other monomers (v) can be used alone a kind, it is possible to use two or more.
《The manufacturing condition of (methyl) acrylic resin (A)》
(methyl) acrylic resin (A) of above-mentioned monomer has been used to be manufactured by solution polymerization process.Because solution is poly-
Legal middle impurity is mixed into less, and the adhesive composition of (methyl) acrylic resin (A) manufactured containing useful this method is fitted
For optical components such as display devices.
Specifically, for example polymer solvent and polymerizable monomer are loaded in reaction vessel, in the inert gas gas such as nitrogen
Polymerization initiator is added under atmosphere, reaction start temperature is set as usual 40~100 DEG C, preferably 50~80 DEG C, ties up reaction system
Hold and reacted 4~24 hours at a temperature of usual 50~90 DEG C, preferably 60~90 DEG C.Gathered by carrying out solution with above-mentioned condition
Close, the weight average molecular weight (Mw) of (methyl) acrylic resin (A) used in the present invention can be made in the range of (a1), together
When can make molecular weight distribution as defined in (a2) in scope.
In the manufacture of acrylic resin (A), polymerization initiator is preferably used, polymerization initiator used herein is preferably
It can be dissolved in polymer solvent or scattered compound.As polymerization initiator, such as azo-initiator, peroxide can be enumerated
Compound Type of Collective initiator.
As azo-initiator, such as 2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-azo two (4- methoxyl groups-
2,4- methyl pentane nitriles), 2-2 '-azo two (2- cyclopropyl propionitrile), 2,2 '-azo two (2,4- methyl pentane nitriles), 2,2 '-it is even
Nitrogen two (2- methylbutyronitriles), 1,1 '-azo two (hexamethylene -1- formonitrile HCNs), 2- (carbamoyl azo) isobutyronitrile, 2- phenyl are even
Nitrogen -4- methoxyl group -2,4- methyl pentane nitriles, two acidified 2,2 '-azos two (2- amidine propanes), 2,2 '-azo two (N, N ' -
Dimethyleneisobutylamidine), 2,2 '-azo two (2- methyl-N- (2- ethoxys)-propionamide), 2,2 '-azo (isobutyramide) two
Hydrate, 4,4 '-azo two (4- cyanopentanoic acids), 2,2'- azos two (2- cyano group propyl alcohol) and (2- of dimethyl -2,2'- azos two
Methylpropionate) etc. azo-compound.
In addition, as peroxide type polymerization initiator, such as TBHP, hydrogen peroxide isopropyl can be enumerated
Benzene, cumyl peroxide, benzoyl peroxide, lauroyl peroxide, peroxidating hexanoyl, di-isopropyl peroxydicarbonate,
The 2- ethylhexyls of dicetyl peroxydicarbonate two, tert-Butyl peroxypivalate, 2,2- bis- (peroxidating 4,4- di-t-butyls cyclohexyl)
Propane, 2,2- bis- (tert-amylcyclohexyls of peroxidating 4,4- bis-) propane, 2,2- bis- (the t-octyl cyclohexyl of peroxidating 4,4- bis-) third
Alkane, 2,2- bis- (bis- α of peroxidating 4,4--cumyl cyclohexyl) propane, 2,2- bis- (peroxidating 4,4- di-t-butyls cyclohexyl) butane
With 2,2- bis- (the t-octyl cyclohexyl of peroxidating 4,4- bis-) butane.
Polymerization initiator can be used alone a kind, it is possible to use two or more.
Polymerization initiator as described above can all be used when polymerizeing and starting, and can also be added several times in the course of the polymerization process
Plus, its adding method is not particularly limited.
Relative to the polymerizable monomer of formation (methyl) acrylic resin (A) of 100 mass parts, with usual 0.001~5
Amount in the range of mass parts, preferably 0.001~3 mass parts uses polymerization initiator.By being triggered with this amount using polymerization
Agent, can adjust the weight average molecular weight (Mw) of (methyl) acrylic resin (A) used in the present invention defined to (a1)
In the range of.In addition, in above-mentioned polymerisation, except polymerization initiator, can also suitably add addition polymerization initiator, chain and turn
Move agent, polymerizable monomer, polymer solvent.
(methyl) acrylic resin used in the present invention is manufactured by solution polymerization process, is used as polymerisation in solution herein
The polymer solvent used in method, can be enumerated aromatic hydrocarbon such as benzene,toluene,xylene；Pentane, n-hexane, normal heptane,
The aliphatic hydrocarbons such as normal octane；The ester ring type hydro carbons such as pentamethylene, hexamethylene, cycloheptane, cyclooctane；Diethyl ether, diisopropyl ether, 1,
The ethers such as 2- dimethoxy-ethanes, butyl oxide, tetrahydrofuran, dioxanes, methyl phenyl ethers anisole, phenetole, diphenyl ether；Chloroform, four chlorinations
The halogenated hydrocarbons such as carbon, 1,2- dichloroethanes, chlorobenzene；The esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate；Third
The ketones such as ketone, MEK, diethyl ketone, methylisobutylketone, cyclohexanone；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-
The amide-types such as methyl pyrrolidone；The nitriles such as acetonitrile, benzonitrile；Sulfoxide types such as dimethyl sulfoxide, sulfolane etc..
Polymer solvent can be used alone a kind, it is possible to use two or more.Present invention preferably uses can dissolve polymerism list
Body and can dissolve generation (methyl) acrylic resin (A) solvent, particularly preferably use the polymerization containing ethyl acetate
Solvent.
《The physical property and content of (methyl) acrylic resin (A)》
The weight average molecular weight (Mw) that the utilization gel permeation chromatography (GPC method) of (methyl) acrylic resin (A) is determined
It is calculated as with polystyrene scaled value in the range of 1,200,000~2,000,000, preferably 1,300,000~1,800,000.If Mw is in the lower limit
More than value, then the cohesiveness of (methyl) acrylic resin (A) is improved, and (methyl) acrylic compounds are come from adhesive phase
The transfer composition of resin (A) is significantly suppressed, and pollution is reduced, so that it is preferred that.In addition, the durability of adhesive phase is also carried
It is high.It is preferred from the point of view of the coating of adhesive composition if Mw is below the higher limit.
In addition, the molecular weight distribution (Mw/Mn) of (methyl) acrylic resin (A) is in the range of 4~9.If Mw/Mn
In the scope, then the content of low-molecular weight is reduced, and therefore the cohesiveness of (methyl) acrylic resin (A) is carried
The transfer composition from (methyl) acrylic resin (A) in height, adhesive phase is significantly suppressed, and pollution is reduced, so that excellent
Choosing.
The glass transition temperature (Tg) of (methyl) acrylic resin (A) can be surveyed by such as differential scanning calorimeter
It is fixed, or calculated by the species and its content ratio of the monomeric unit for constituting (methyl) acrylic resin (A) using Fox formula
Go out.For example, can be reached with the glass transition temperature (Tg) of (methyl) acrylic resin (A) tried to achieve by Fox formula logical
Often -70~10 DEG C, preferably -60~0 DEG C of condition synthesizes (methyl) acrylic resin (A).By each monomer structure in Fox formula
Into homopolymer glass transition temperature can be used for example《Polymer handbook》(Polymer Handbook) fourth edition
Described numerical value in (Wiley-Interscience 2003).
In the present invention acid number of acrylic resin obtained as described above (A) need in below 2mg KOH/g, preferably 0~
1mg KOH/g, more preferably 0mg KOH/g.In addition, acid number herein refers to neutralize 1g (methyl) acrylic resin (A) institute
The mg numerical value of the potassium hydroxide needed.(methyl) acrylic resin (A) if content in the scope, such as by ITO
When the metal oxides such as film are used as clung body, the corrosion of clung body can be reduced.In addition, the bonding force after heat treatment can be suppressed
Rise.In order that acrylic resin (A) have the acid number, can enumerate for example with《Monomer (iii) containing acidic group》Middle note
Content in the range of load uses monomer (iii) as the composition for constituting acrylic resin (A).
(methyl) acrylic resin (A) obtained as above is generally obtained with the state being dissolved in polymer solvent, now
The concentration of (methyl) acrylic resin (A) is usually 10~80 mass % in polymer solvent, more preferably 15~70 mass %,
Particularly preferably 15~50 mass %.
(methyl) acrylic resin (A) being dissolved in like this in polymer solvent can be by adding poor solvent and from polymerization
Solvent is used after separating out separation, and the state that can also be dissolved in polymer solvent is used in following process.
[HDI classes crosslinking agent (B)]
The adhesive composition of the present invention contains HDI classes crosslinking agent (B).(methyl) propylene is made by HDI classes crosslinking agent (B)
Acid resin (A) is crosslinked, and can be formed crosslinked (network polymers), can be obtained the adhesive phase of excellent heat resistance.By making
With HDI classes crosslinking agent (B), can suppress it is heat-resisting after bonding force rise, in addition, adhesive phase softens and wetability improves,
Undesirable condition is not likely to produce with the laminating engineering of the adherends such as functional membrane to optics.
As HDI class crosslinking agents, for example, as the HDI class crosslinking agents in 1 molecule with 2 NCOs, can enumerate
Hexamethylene diisocyanate, 2,2,4- trimethyl -1,6- hexamethylene diisocyanates.As having 3 isocyanides in 1 molecule
The HDI class crosslinking agents of perester radical, can enumerate the biuret body or isocyanuric acid ester body and three hydroxyls of hexamethylene diisocyanate
The reaction product (3 molecule addition products of such as hexamethylene diisocyanate) of methylpropane and hexamethylene diisocyanate,
TPA-100 (the chemical combination names of Asahi Chemical Corp (Asahi Chemical Industry ケ ミ カ Le ズ (strain)) system can specifically be enumerated；Six methylenes
The isocyanuric acid ester body of group diisocyanate), Nippon Polyurethane Industry Co., Ltd.'s (Japanese Port リ ウ レ タ Application (strain)) system U
ロ ネ ー ト HX (3 molecule addition products of hexamethylene diisocyanate) etc..From the reaction with (methyl) acrylic resin (A)
Property it is high from the point of view of, there is the HDI class crosslinking agents of 3 NCOs in more preferably 1 molecule.
HDI classes crosslinking agent (B) can be used alone a kind, it is possible to use two or more.
In the adhesive composition of the present invention, the content of HDI crosslinking agents (B) can be according to (methyl) acrylic resin (A)
Suitably selected, above-mentioned (methyl) acrylic resin (A) relative to 100 mass parts is preferably 2~15 mass parts, more excellent
Elect 2~10 mass parts as.By blending crosslinking agent (B) within the above range so that the gel fraction of adhesive compositions is 90.0
Translating into from (methyl) acrylic resin (A) in~99.9 mass %, the adhesive phase formed by adhesive composition
Divide and significantly suppressed, pollution is reduced.In addition, adhesive phase can obtain sufficient heat resistance using the cohesiveness of adhesive phase,
Flexibility and cohesive are excellent.
HDI classes crosslinking agent (B), which has, is combined with the structure of NCO in the end of alkylidene, alkylidene it is removable
Property it is high so that in the state of having NCO combination in end, the NCO of other ends can be than relatively freely revolving
Turn, therefore reactivity is uprised.In addition, the NCO of two ends reacts and formd (methyl) acrylic compounds of cross-linked structure
Resin (A) does not also use rigid structure, so that adhesive phase becomes with flexibility.
[organic solvent (C)]
The adhesive composition of the present invention preferably comprises organic solvent (C) to adjust its coating.As organic molten
Agent, is preferably directly used《The manufacturing condition of (methyl) acrylic resin (A)》The polymer solvent illustrated in one column is as organic
Solvent.For example, can be by the monomer solution containing (methyl) acrylic resin (A) and polymer solvent and HDI classes crosslinking agent (B)
Mix to prepare adhesive composition.In the adhesive composition of the present invention, the content of organic solvent is usually 20~90 matter
Measure %, preferably 30~80 mass %.
In addition, " solid constituent " in the present invention refers in composition contained in adhesive composition except above-mentioned organic
Whole compositions beyond solvent (C), " solid component concentration " refers to adhesive group of the above-mentioned solid constituent relative to 100 mass %
The ratio of compound.
[additive]
The adhesive composition of the present invention in the range of effect of the present invention is not damaged, may be used also in addition to mentioned component
Contain antistatic agent, antioxidant, light stabilizer, preventing metal corrosion agent, tackifier, plasticizer, crosslinking accelerator, interfacial activity
(methyl) acrylic resin and heavy industry remover (Japanese beyond agent, (A)：リ ワ ー Network drug) etc. other compositions.
[preparation of surface protection film adhesive composition]
The surface protection film adhesive composition of the present invention can be by using known method to (methyl) propylene
Acid resin (A), HDI classes crosslinking agent (B) and other compositions as needed are mixed to prepare.Can enumerate for example to containing
In the monomer solution of (methyl) acrylic resin obtained during useful solution polymerization process synthesis (methyl) acrylic resin (A)
The method for blending HDI classes crosslinking agent (B) and other compositions as needed.
The surface protection film of the present invention is with adhesive composition for example by the range of with 30.0~99.9 mass %
The amount polymerizable monomer that contains (methyl) alkyl acrylate of alkyl carbon number below 4 carry out polymerisation in solution and manufacture (first
Base) acrylic resin (A) process and to the incorporation isocyanide of hexa-methylene two in (methyl) acrylic resin (A)
Esters of gallic acid crosslinking agent (B) so that the adhesive phase formed by surface protection film with adhesive composition gel fraction 90.0~
Process in the range of 99.9 mass % is manufactured.
[adhesive phase]
Adhesive phase is formed by above-mentioned adhesive composition.For example it is anti-by carrying out the crosslinking in above-mentioned adhesive composition
Should come obtain described adhesive layer, in particular by with HDI classes crosslinking agent (B) make (methyl) acrylic resin (A) hand over
Join to obtain described adhesive layer.
The formation condition of adhesive phase is for example as described below.The adhesive composition of the present invention is coated on membranaceous supporting mass
On, temperature is different because of solvent species, generally 50~150 DEG C, preferably carried out at 60~100 DEG C usual 1~10 minute, preferably
The drying of 2~7 minutes forms film to remove solvent.The average film thickness of dry coating is usually 5~75 μm, preferably 10~
50μm。
Adhesive phase is preferably formed under the following conditions.The adhesive composition of the present invention is coated on membranaceous supporting mass
On, after attaching stripping film on the film formed with above-mentioned condition, at usual 5~60 DEG C, preferably 15~40 DEG C and usual 30~
Conserved in the environment of 70%RH, preferably 40~70%RH usual more than 3 days, preferably 7~10 days.If entered with above-mentioned cooking conditions
Row crosslinking, then can be efficiently formed crosslinked (network polymers).
As the coating method of adhesive composition, can using known method, for example spin-coating method, cutter painting method, rolling method,
Stick coating method, scraper coating, die coating method, gravure coating method etc..It is defined to reach by coating adhesive composition in this way
Thickness simultaneously removes solvent, while curing coating layer, can form adhesive phase.
Membranaceous supporting mass and stripping film are illustrated in [surface protection film] column.
The gel fraction of adhesive phase formed by the adhesive composition of the present invention is 90.0~99.9 mass %, more excellent
Elect 95.0~99.9 mass % as.If the gel fraction of adhesive phase is within the above range, from contained by adhesive phase
The transfer composition of (methyl) acrylic resin (A) is significantly suppressed, and pollution is reduced, so that it is preferred that.In addition, adhesive phase is solidifying
Glue fraction can be adjusted to preferred scope by the blended amount and reaction condition of HDI classes crosslinking agent (B).
In addition, the adhesive phase of the present invention is due to having sufficiently high low speed peeling force with sufficient bonding force, separately
External high speed is easily peeled off when peeling off.The low speed peeling force of the adhesive phase of the present invention is generally in more than 0.05N/25mm, preferably
For 0.05~0.5N/25mm.High speed peeling force under A-stage is generally in below 1.5N/25mm, preferably 0.5~1.5N/
25mm.In addition, the high speed peeling force after high-temperature technology is generally in below 2.5N/25mm, preferably 0.5~2.5N/25mm.
In addition, low speed peeling force and high speed peeling force are measured according to the method described in embodiment.
(surface protection film)
The surface protection film of the present invention has the adhesive phase formed by above-mentioned surface protection film with adhesive composition.Table
Surface protective film can also have stripping film, can enumerate for example on the face of a side of membranaceous supporting mass formed described adhesive layer,
The surface protection film of stripping film is fitted with the face of the opposing party of the membranaceous supporter without described adhesive layer.
As membranaceous supporting mass, the polyester film such as polyethylene terephthalate (PET) can be enumerated；It is polyethylene, poly-
The membranaceous supporting mass such as the polyolefin films such as propylene, vinyl-vinyl acetate copolymer.Wherein, from the transparency and thermal dimensional stability
From the point of view of, preferably PET film.
As stripping film, the polyester film such as PET can be enumerated；Polyethylene, polypropylene, vinyl-vinyl acetate copolymer
Deng plastic foils such as polyolefin films.
The formation condition and gel fraction of adhesive phase are identical with the condition described in [adhesive phase] one column.
The thickness of adhesive phase is usually 5~75 μm, preferably 10~50 μm from the viewpoint of bond properties is maintained.It is right
There is no particular limitation for the thickness of membranaceous supporting mass and stripping film, usually 10~100 μm, preferably 25~100 μm.
The surface protection film of the present invention can be mainly by fitting in liquid crystal display, plasma scope, surface conduction
The surface of display device as described above is protected on surfaces of optical display such as type electron emission display device (SED) etc..Separately
Outside, be not limited to this display device, can also fit in the polarizer for constituting this display device, polarizer, liquid crystal cell, thoroughly
The surface of these optical components is protected on the surface of the component parts of the display devices such as prescribed electrode plate.
The surface protection film of the present invention can suppress the corrosion of metal oxide and suppress the bonding force rise after heat treatment,
Therefore it is particularly suitable for being fitted in the surface for the ito film for needing high temperature manufacturing process.
Embodiment
More specific description is carried out to the present invention below based on embodiment, but the present invention is not limited to these embodiments.With
In the record of lower embodiment etc., unless otherwise instructed, then " part " expression " mass parts ".
〔GPC〕
Using gel permeation chromatography (GPC) method, dividing equally again for (methyl) acrylic resin (A) is obtained under the following conditions
Son amount (Mw) and number-average molecular weight (Mn).
Determine device：HLC-8320GPC (TOSOH Co., Ltd (East ソ ー (strain)) makes)
The composition of GPC posts：Following 4 pedestals (being TOSOH Co., Ltd's system)
(1) TSKgel HxL-H (guard column)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow velocity:1.0ml/ minute
Column temperature：40℃
Sample solution concentration：1.5% (w/v) (being diluted with tetrahydrofuran)
Mobile phase solvent：Tetrahydrofuran
Polystyrene standard converts
(acid number)
The mg numerical value of potassium hydroxide needed for calculating neutralization 1g acrylic resins, calculates acid number.
[synthesis example A1]
95.0 parts of propylene are added into the reaction unit for possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe
Sour N-butyl, 5.0 parts of acrylic acid 4- hydroxybutyls and 100 parts of ethyl acetate solvents, import nitrogen while being warming up to 80
℃.Then, the 2 of 0.1 part of addition, 2 '-azodiisobutyronitrile, in a nitrogen atmosphere in the polymerisation of 80 DEG C of progress 6 hours.Instead
After should terminating, it is diluted with ethyl acetate, has prepared the polymer solution that solid component concentration is 20 mass %.Gained (first
Base) acrylic resin A1 Mw for 1,600,000, Mw/Mn be 6.0.Calculated acid number is 0.
[synthesis example A2]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A2 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A3]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A3 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A4]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A4 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A5]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A5 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A6]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A6 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A7]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A7 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A8]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-1, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A8 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-1.
[synthesis example A9]
Except being changed to 130 mass by the record incorporation polymerizable monomer in table 1-2, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A9 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-2.
[synthesis example A10]
Except being changed to 160 mass by the record incorporation polymerizable monomer in table 1-2, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A10 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-2.
[synthesis example A11]
95.0 parts of propylene are added into the reaction unit for possessing mixer, reflux cooler, thermometer and nitrogen ingress pipe
Sour N-butyl, 5.0 parts of acrylic acid 4- hydroxybutyls and 130 parts of ethyl acetate solvents, import nitrogen while being warming up to 80
℃.Then, the 2 of 0.1 part of addition, 2 '-azodiisobutyronitrile starts polymerisation in a nitrogen atmosphere.Reaction starts 3 hours
Afterwards, the 2 of additional 0.1 mass parts, 2 '-azodiisobutyronitrile further carries out the polymerisation of 3 hours at 80 DEG C.Reaction knot
Shu Hou, is diluted with ethyl acetate, and it is 20 matter to have prepared the solid component concentration containing (methyl) acrylic resin A11
Measure % polymer solution.As a result it is shown in table 1-2.
[synthesis example A12]
Except in by table 1-2 record incorporation polymerizable monomer in addition to, carried out in the same manner as synthesis example A1 polymerisation and
The preparation of polymer solution, it is the poly- of 20 mass % to be contained (methyl) acrylic resin A12 solid component concentration
Polymer solution.As a result it is shown in table 1-2.
[synthesis example A13]
Except in by table 1-2 record incorporation polymerizable monomer in addition to, carried out in the same manner as synthesis example A1 polymerisation and
The preparation of polymer solution, it is the poly- of 20 mass % to be contained (methyl) acrylic resin A13 solid component concentration
Polymer solution.As a result it is shown in table 1-2.
[synthesis example A14]
Except being changed to 160 mass by the record incorporation polymerizable monomer in table 1-2, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A14 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-2.
[synthesis example A15]
Except being changed to 115 mass by the record incorporation polymerizable monomer in table 1-2, by the incorporation of ethyl acetate solvent
Beyond part, the preparation of polymerisation and polymer solution is carried out in the same manner as synthesis example A1, is contained (methyl) acrylic acid
Resinoid A15 solid component concentration is 20 mass % polymer solution.As a result it is shown in table 1-2.
[table 1-1]
Table 1-1
[table 1-2]
Table 1-2
[embodiment 1]
(1) preparation of adhesive composition
Will as obtained by synthesis example A1 (methyl) acrylic polymer solution (the mass % of solid component concentration 20) with make
For (B1) of HDI classes crosslinking agent (B)：" TPA-100 " mixing of Asahi Chemical Corp, has obtained adhesive combination
Thing.In addition, the ratio of each composition is relative to the tree contained by (methyl) acrylic polymer solution as obtained by synthesis example A1
A1100 parts of fat, the amount (being solid constituent value) that (B1) is 5 parts.
(2) making of surface protection film
After froth breaking, with scraper in the polyethylene terephthalate film (PET film) Jing Guo lift-off processing with 25 DEG C
The adhesive composition that liquid temperature coating is obtained by above-mentioned (1), is dried 3 minutes at 90 DEG C, forms the painting that dry film thickness is 20 μm
Film.The PET film further fitted on the reverse side of the sticking veneer of the PET film of film Jing Guo lift-off processing, 23 DEG C/50%
Stand after being cured within 7 days, obtained with by table of the thickness clamped by 2 PET films for 20 μm of adhesive phase under RH environment
Surface protective film.
[embodiment 2~10, comparative example 1~11]
It is same with embodiment 1 in addition to the blending composition in embodiment 1 is changed by table 2-1 and table 2-2 record
Adhesive composition and surface protection film have been obtained sample.
In addition, each material in table 2-1 and table 2-2 is as follows.
HDI classes crosslinking agent (B) and other crosslinking agents
B1：The isocyanuric acid ester body of hexamethylene diisocyanate
(Asahi Chemical Corp's system, TPA-100)
B2：3 molecule addition products of hexamethylene diisocyanate
(Nippon Polyurethane Industry Co., Ltd.'s system, U ロ ネ ー ト HX)
B3：The trimethylolpropane adduct of toluene di-isocyanate(TDI)
(Nippon Polyurethane Industry Co., Ltd.'s system, U ロ ネ ー ト L, the mass % of solid component concentration 75)
B4：M xylene diisocyanate class adduct type
(Mitsui Chemicals, Inc's (Mitsui Chemicals (strain)) system, D-120N)
B5：Epoxies curing agent
(Mitsubishi Gas Chemical Co., Ltd (Mitsubishi ガ ス chemistry (strain)) system, テ ト ラ ッ De C)
[evaluation]
[gel fraction]
From the surface protection film collection about 0.1g obtained by embodiment comparative example adhesive phase is placed in sample bottle, plus
After entering 30mL ethyl acetate and shaking 4 hours, the content of the sample bottle was carried out with 200 purposes stainless steel wire netting
Filter, to the drying of the residue progress 2 hours on wire netting at 100 DEG C, determines dry weight.Bonding is obtained using following formula
The gel fraction of oxidant layer.
Gel fraction (%)=(dry weight/adhesive phase collection weight) × 100 (%)
(ITO corrosivity)
The surface protection film as obtained by embodiment comparative example is cut into 10mm × 60mm, unilateral stripping film is shelled
From, then conform to be cut into 10mm × 100mm ITO evaporation PET film, implemented 20 minutes with the condition of 50 DEG C, 5atm
Autoclave process.Then, at room temperature stand 1 hour after, in the environment of 60 DEG C, 90%RH place 500 hours, with 23 DEG C,
After 65%RH condition stands 1 hour, determine the resistance value of ITO evaporation films, obtain relative to measured in advance be not carried out it is above-mentioned
The rate of change of the resistance value of the resistance value of the surface protection film of processing, by following standard evaluation.In addition, using analyzer (three Hes
Electric gauge Co., Ltd. (three and Electricity mood Meter devices (strain)) system, digital multimeter (デ ジ タ Le マ Le チ メ ー タ ー) PC510)
Determine resistance value.
(standard)
·AA：The rate of change of resistance value is less than 10%.
·CC：The rate of change of resistance value is more than 10%.
(contaminative)
The PET film that have passed through lift-off processing is peeled off from the surface protection film as obtained by embodiment comparative example, is cut into
2.5cm × 15cm, is attached on stainless steel.After being placed 24 hours at 80 DEG C, diaphragm is peeled off from stainless steel plate, with mesh
Depending on confirming whether the stainless steel surface of laminating over-protective film has pollution, evaluated by following standard.
(standard)
·AA：Do not observe pollution completely
·BB：It was observed that a small amount of is dirty caused by adhesive phase
·CC：It was observed that obvious pollute caused by adhesive phase
(low speed peeling force)
The surface protection film as obtained by embodiment comparative example is cut into 25mm × 150mm, peels off have passed through stripping respectively
From the PET film of processing, attach in stainless steel plate.It placed in the environment of 25 DEG C, humidity 50% 24 hours.Afterwards, with
The peeling rate of 300mm/ minutes stretches one end to 180 ° of directions, is low speed peeling force by masterpiece when starting to be peeling.
(high speed peeling force)
The surface protection film as obtained by embodiment comparative example is cut into 25mm × 150mm, peels off have passed through stripping respectively
From the PET film of processing, attach in stainless steel plate.It placed in the environment of 25 DEG C, humidity 50% 24 hours.Afterwards, with
The peeling rate of 30000mm/ minutes stretches one end to 180 ° of directions, and masterpiece when starting to be peeling is shelled for the high speed at initial stage
From power.
The surface protection film as obtained by embodiment comparative example is cut into 25mm × 150mm, peels off have passed through stripping respectively
From the PET film of processing, attach in stainless steel plate.It placed in the environment of 150 DEG C 1 hour.Afterwards, with 30000mm/ minutes
Peeling rate stretches one end to 180 ° of directions, is the high speed peeling force after heat-resisting by masterpiece when starting to be peeling.
(wetability)
The surface protection film as obtained by embodiment comparative example is cut into 40mm × 150mm, test film has been made.Not
The two ends of test film are held on rust steel plate and close to stainless steel plate so that the center of only test film is contacted with stainless steel plate, so
The time untill the two ends of test film, the overall infiltration spread (closely sealed) on stainless steel of determination test piece is decontroled afterwards, by following
Standard is evaluated.
(standard)
·AA：Less than 20 seconds
·BB：20 seconds less than 60 seconds
·CC：More than 60 seconds
[table 2-1]
Table 2-1
The unit of the numerical value of ※ adhesive compositions is mass parts.
[table 2-2]
Table 2-2
The unit of the numerical value of ※ adhesive compositions is mass parts.
Claims (3)
1. surface protection film adhesive composition, it is containing (methyl) acrylic resin (A) and the isocyanide of hexa-methylene two
The surface protection film adhesive composition of esters of gallic acid crosslinking agent (B), it is characterised in that
(methyl) acrylic resin (A) passes through to containing alkyl carbon number with the amount in the range of 30.0~99.9 mass %
The polymerizable monomer of (methyl) alkyl acrylate below 4 carries out polymerisation in solution and obtain, and have following (a1), (a2) and
(a3) characteristic,
With the gel fraction of adhesive phase that is formed by the surface protection film with adhesive composition in 90.0~99.9 matter
Amount in the range of amount % contains the hexamethylene diisocyanate class crosslinking agent (B),
(a1) the weight average molecular weight Mw of the polystyrene conversion determined by gel permeation chromatography (GPC method) is 1,200,000~2,000,000
In the range of,
(a2) molecular weight distribution mw/mn is in the range of 4~9,
(a3) acid number is in below 2mg KOH/g.
2. surface protection film adhesive composition as claimed in claim 1, it is characterised in that relative to (methyl) third
The mass parts of olefin(e) acid resinoid (A) 100, the content of the hexamethylene diisocyanate class crosslinking agent (B) is in 2~15 mass parts
In the range of.
3. surface protection film, it is formed on the face of at least one party with membranaceous supporting mass and in the membranaceous supporting mass
Adhesive phase surface protection film, it is characterised in that
Described adhesive layer is formed as the surface protection film described in claim 1 or 2 with adhesive composition.
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| JP2014-227194 | 2014-11-07 | ||
| JP2014227194 | 2014-11-07 | ||
| PCT/JP2015/080329 WO2016072324A1 (en) | 2014-11-07 | 2015-10-28 | Pressure-sensitive adhesive composition for surface protection film and surface protection film |
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| JP (1) | JP6348607B2 (en) |
| KR (1) | KR102178126B1 (en) |
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| JP7166783B2 (en) * | 2018-04-25 | 2022-11-08 | 藤森工業株式会社 | Adhesive composition solution, method for producing adhesive film, method for producing optical film with adhesive layer, method for producing polarizing plate with adhesive layer |
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| JP2013127012A (en) * | 2011-12-16 | 2013-06-27 | Toyo Ink Sc Holdings Co Ltd | Adhesive, adhesive sheet and display |
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- 2015-10-28 KR KR1020177011058A patent/KR102178126B1/en active IP Right Grant
- 2015-10-28 WO PCT/JP2015/080329 patent/WO2016072324A1/en active Application Filing
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- 2015-10-28 CN CN201580058487.1A patent/CN107075332B/en active Active
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| CN101313043A (en) * | 2005-11-21 | 2008-11-26 | 综研化学株式会社 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| CN101508875A (en) * | 2008-02-15 | 2009-08-19 | 日东电工株式会社 | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| CN102131881A (en) * | 2008-08-20 | 2011-07-20 | Lg化学株式会社 | Adhesive agent |
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| Publication number | Publication date |
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| TW201625763A (en) | 2016-07-16 |
| KR20170084032A (en) | 2017-07-19 |
| CN107075332B (en) | 2019-03-01 |
| KR102178126B1 (en) | 2020-11-12 |
| TWI708823B (en) | 2020-11-01 |
| WO2016072324A1 (en) | 2016-05-12 |
| JP6348607B2 (en) | 2018-06-27 |
| JPWO2016072324A1 (en) | 2017-08-10 |
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