CN109844052A - Protective film adhesive composition and protective film - Google Patents

Protective film adhesive composition and protective film Download PDF

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Publication number
CN109844052A
CN109844052A CN201780001583.1A CN201780001583A CN109844052A CN 109844052 A CN109844052 A CN 109844052A CN 201780001583 A CN201780001583 A CN 201780001583A CN 109844052 A CN109844052 A CN 109844052A
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China
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methyl
mass
protective film
acrylic acid
monomer
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CN201780001583.1A
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CN109844052B (en
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堀崇晴
鸭井彬
藤川春奈
中野宏人
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TOKYO
Nippon Carbide Industries Co Inc
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TOKYO
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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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The protective film of one embodiment of the present invention adhesive composition includes (methyl) acrylic acid series polymeric compounds, crosslinking agent and antistatic agent; the acid value of above-mentioned (methyl) acrylic acid series polymeric compounds is 9mgKOH/g~65mgKOH/g; and; relative to the quality of entire infrastructure unit, the containing ratio of the structural unit from the monomer with polyalkylene oxide chain is more than 1 mass % and less than 20 mass %.

Description

Protective film adhesive composition and protective film
Technical field
This disclosure relates to a kind of protective film adhesive composition and protective film.
Background technique
In general, the optical component of polarizing film used in liquid crystal display device etc. protective film multi-purpose greatly is protected. Protective film prevents the optical component being easy to produce in each process such as punching processing, inspection, conveying, the assembling of LCD panel The pollution and damage on surface are removed in the stage of the protection on the surface for not needing optical component and are removed.
If from optical component remove protective film when generate electrostatic, be easy to produce dust etc. be attached to optical component or The unfavorable condition that the circuit of liquid crystal display device is destroyed.Therefore, the electrostatic for preventing from generating when removing is required to protective film Property (hereinafter also referred to as " antistatic property ").
Furthermore, it desired to the adhesive phase of protective film have adherend need protect during will not be on the surface of adherend The upper adhesiveness for generating deviation or the degree to fall off from the surface of adherend, and, it is desirable that it is not required in adherend to be protected Stage is easy to remove (hereinafter also referred to as " fissility ") from adherend.
Moreover, in recent years, as the purpose for improving operating efficiency, having from adherend removing protective film in high speed stripping conditions Under (for example, 30m/ minutes) carry out trend, it is desirable that even if high speed remove, also can easily from adherend removing (hereinafter, Also referred to as " high-rate release property ").
As the antistatic property adhesive composition of excellent antistatic property, disclosing includes that (methyl) alkyl acrylate is The acid value of principal component be 29 (methyl) acrylic acid series polymeric compounds below and fluorine-containing imines lithium salts adhesive composition (for example, Referring to Japanese Unexamined Patent Publication 2005-306937 bulletin).
In addition, as excellent antistatic property, reducing to by the adhesive composition of the pollution of protective, packet is disclosed Alkali metal containing salt, use as monomer component 15 weight of weight %~100 % of (methyl) acrylic acid alkylene oxide adduct it is viscous Mixture composite (for example, referring to Japanese Unexamined Patent Publication 2005-314579 bulletin).
Summary of the invention
The antistatic property adhesive composition recorded in Japanese Unexamined Patent Publication 2005-306937 bulletin is because of (methyl) acrylic acid Based polymer contains acidic-group, so while the polarity effect of acidic-group causes wetability to be easy due to the material of adherend Variation.When therefore, using the antistatic property adhesive composition recorded in Japanese Unexamined Patent Publication 2005-306937 bulletin, it is difficult to The stripping conditions when material of adherend irrelevantly removes high speed are constant.Also, use Japanese Unexamined Patent Publication 2005-306937 When the antistatic property adhesive composition recorded in number bulletin, antistatic property is deteriorated due to the material of adherend sometimes.In addition, making With the antistatic property bonding sheet for the adhesive composition recorded in Japanese Unexamined Patent Publication 2005-314579 bulletin sometimes because of adherend Material and be difficult to obtain sufficient antistatic property, and cannot get high-rate release property.
Therefore, in order to enable previous protective film adhesive composition to have when high speed is removed easily from being glued The bonding force and antistatic property of the degree of object removing need to cooperate the material of adherend and change the composition of adhesive.Adherend Material it is numerous, therefore be actually difficult to mate to the material of adherend to prepare adhesive composition, so seeking one The adhesive composition of the material of the not interdependent adherend of kind.
The disclosure is to carry out in view of the foregoing.
The one embodiment of the present invention project to be solved is to provide a kind of protective film adhesive composition and protection Film, no matter the material of adherend, high-rate release property and antistatic property are all excellent.
Specific means for solving the above subject includes following form.
A kind of protective film adhesive composition of 1 > of < includes (methyl) acrylic acid series polymeric compounds, crosslinking agent and antistatic The acid value of agent, above-mentioned (methyl) acrylic acid series polymeric compounds is 9mgKOH/g~65mgKOH/g, also, relative to entire infrastructure list The quality of member, the containing ratio of the structural unit from the monomer with polyalkylene oxide chain are more than 1 mass % and less than 20 mass %.
2 > of < protective film adhesive composition according to 1 > of <, wherein above-mentioned (methyl) acrylic polymeric Object contains the structural unit of the following general formula (1) expression.
In general formula (1), R1Indicate hydrogen atom or methyl.L is indicated by former selected from alkylidene, arlydene, carbonyl and oxygen The linking group of the divalent of at least one kind of composition in son.
3 > of < protective film adhesive composition according to 2 > of < 1 > or <, wherein above-mentioned (methyl) propylene Sour based polymer contains the structural unit from (methyl) alkyl acrylate, above-mentioned relative to the quality of entire infrastructure unit The containing ratio of structural unit from (methyl) alkyl acrylate is 65 mass of mass %~99 %.
4 > of < protective film adhesive composition according to any one of 1 > of <~<, 3 >, wherein further packet (methyl) acrylic oligomers for being 3000~20000 containing weight average molecular weight, relative to above-mentioned (methyl) acrylic polymeric 100 mass parts of object, the content of above-mentioned (methyl) acrylic oligomers are 0.05 mass parts~5.00 mass parts.
5 > of < protective film adhesive composition according to 4 > of <, wherein above-mentioned (methyl) acrylic acid series is oligomeric Object contains the structural unit from the monomer with polyalkylene oxide chain, above-mentioned from tool relative to the quality of entire infrastructure unit The containing ratio for having the structural unit of the monomer of polyalkylene oxide chain is 5 mass of mass %~30 %.
6 > of < protective film adhesive composition according to any one of 1 > of <~<, 5 >, wherein above-mentioned crosslinking Agent is metallo-chelate.
A kind of protective film of 7 > of <, has adhesive phase and substrate, and above-mentioned adhesive phase is any one of 1 > of <~<, 6 > The cross-linking agent of the protective film adhesive composition.
According to an embodiment of the present invention, it is capable of providing a kind of protective film adhesive composition and protective film, no By adherend material how, high-rate release property and antistatic property are all excellent.
Detailed description of the invention
Fig. 1 is the explanatory diagram for illustrating the method for bonding force and antistatic property when evaluation high speed is removed.
Specific embodiment
Hereinafter, the protective film to one embodiment of the present invention is carried out specifically with the agent of adhesive group at object and protective film It is bright.It should be noted that "~" in numberical range indicates the numerical value of the front and back comprising "~" in the present invention.
In this specification, the amount of each ingredient in composition is unless otherwise specified, it is meant that deposits in the composition In a variety of substances comparable with each ingredient, the total amount of many kinds of substance present in composition.
In this specification, (methyl) acrylic acid series polymeric compounds or (methyl) acrylic oligomers indicate to constitute its list In body is at least the polymer or oligomer of the monomer with (methyl) acryloyl group as the monomer of principal component.As master The monomer of ingredient refers to the maximum monomer of containing ratio (quality %) in the monomer for constituting polymer or oligomer.(methyl) propylene The containing ratio that sour based polymer for example can be the structural unit from (methyl) acrylate monomer as principal component is complete The polymer of the 50 mass % or more of portion's structural unit.
In this specification, " (methyl) acrylic acid " means to include both " acrylic acid " and " methacrylic acid ", " (first Base) acrylate " mean to include both " acrylate " and " methacrylate ", " (methyl) acryloyl group " means Including both " acryloyl group " and " methylacryloyl ".
" protective film adhesive composition "
The protective film of one embodiment of the present invention is wrapped with adhesive composition (hereinafter also referred to as " adhesive composition ") Containing (methyl) acrylic acid series polymeric compounds, crosslinking agent and antistatic agent, the acid value of (methyl) acrylic acid series polymeric compounds is 9mgKOH/g~65mgKOH/g, also, the quality relative to entire infrastructure unit, from the monomer with polyalkylene oxide chain The containing ratio of structural unit is more than 1 mass % and less than 20 mass %.
Since adhesive composition has above-mentioned composition, no matter so obtaining the material of adherend, high-rate release property The all excellent protective film with antistatic property.The reason is not yet clear for this, but can speculate as follows.
In general, the fissility when high speed removing of protective film has becoming for the material for significantly depending on adherend Gesture.Especially in the adhesive composition containing the structural unit from the monomer with acidic-group, due to acidic-group Polarity effect and to the wetability of adherend change, because of the material of adherend, the bonding force of performance is sometimes different.Accordingly, there exist High speed is difficult to the trend removed when removing.In addition, in the adhesive composition comprising the polymer that acid value is 1mgKOH/g or more There are the trend that antistatic property is easily reduced.
The adhesive composition of one embodiment of the present invention is speculated because containing the quality relative to entire infrastructure unit The containing ratio of structural unit from the monomer with polyalkylene oxide chain is more than 1 mass % and less than (methyl) third of 20 mass % Olefin(e) acid based polymer, so inhibiting the polarity effect due to acidic-group and being easy the surface free energy of adhesive phase got higher. Structural unit from the monomer with polyalkylene oxide chain is easy largely to be present in the interface of adherend and adhesive composition.Cause This, even if (the first for being 9mgKOH/g~65mgKOH/g comprising acid value in the adhesive composition of one embodiment of the present invention Base) acrylic acid series polymeric compounds, it is also able to suppress the variation of the wetability to adherend caused by the polarity effect of acidic-group, No matter the material or state of adherend, can play constant bonding force.In addition, one embodiment of the present invention Adhesive composition is because the acid value of (methyl) acrylic acid series polymeric compounds and includes crosslinking agent in above-mentioned range, so tool There is appropriate fissility, in addition, the hardness for the degree that bonding force when high speed is removed moderately becomes smaller can be set as, so having height The excellent trend of fast fissility.
Also, the adhesive composition of one embodiment of the present invention is because comprising antistatic agent, even if (methyl) propylene The acid value of sour based polymer is also able to suppress the reduction of antistatic property in above-mentioned range.Especially because and to specifically containing (methyl) acrylic acid series polymeric compounds and antistatic agent for thering is rate to contain the structural unit from the monomer with polyalkylene oxide chain, institute Further suppress the reduction of antistatic property to exist, and though the material of substrate how all excellent trend of antistatic property.
In this way, thus it is speculated that no matter the material of the protective film adherend formed by the adhesive composition of one embodiment of the present invention How is matter, and high-rate release property and antistatic property are all excellent.
Hereinafter, being illustrated to the details of each ingredient of the adhesive composition of one embodiment of the present invention.
< (methyl) acrylic acid series polymeric compounds >
The adhesive composition of one embodiment of the present invention includes that acid value is 9mgKOH/g~65mgKOH/g also, phase For the quality of entire infrastructure unit, the containing ratio of the structural unit from the monomer with polyalkylene oxide chain is more than 1 mass % And less than in (methyl) acrylic acid series polymeric compounds of 20 mass % (hereinafter also referred to as " specific (methyl) acrylic acid series polymeric compounds ") It is at least one kind of.The adhesive composition of one embodiment of the present invention, which can according to need, to be further included and specific (methyl) Different (methyl) acrylic acid series polymeric compounds of acrylic acid series polymeric compounds.
Specific (methyl) acrylic acid series polymeric compounds contain the structural unit from the monomer with polyalkylene oxide chain.As poly- Alkylene oxide chain can enumerate polyethylene oxide chain, polypropylene oxide chain etc..No matter all being obtained sufficiently from the material of adherend Antistatic property from the viewpoint of, as polyalkylene oxide chain, preferably polyethylene oxide chain.
As the monomer with polyalkylene oxide chain, for example, acrylic acid 2- (ethoxy ethoxy) ethyl ester can be enumerated, gathered Ethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylic acid Ester, polypropylene glycol (methyl) acrylate and methoxy poly (ethylene glycol) (methyl) acrylate.
Wherein, no matter from the viewpoint of how antistatic property and high-rate release property being played from the material of adherend, As the monomer with polyalkylene oxide chain, preferably methoxy poly (ethylene glycol) (methyl) acrylate or methoxyl group polypropylene glycol (methyl) acrylate, more preferable methoxy poly (ethylene glycol) (methyl) acrylate.
As the average addition molal quantity of the alkylene oxide unit in polyalkylene oxide chain, preferably 2 moles~25 moles, no matter from From the viewpoint of how the material of adherend also can obtain sufficient antistatic effect, more preferable 4 moles~15 moles.
It should be noted that the average addition molal quantity of the alkylene oxide unit in polyalkylene oxide chain means in included monomer Alkylene oxide unit additional molal quantity average value.
Structural unit from the monomer with polyalkylene oxide chain contained in specific (methyl) acrylic acid series polymeric compounds Containing ratio is more than 1 mass % and less than 20 mass % relative to the quality of entire infrastructure unit.
If the containing ratio of the structural unit from the monomer with polyalkylene oxide chain be 1 mass % hereinafter, if because being glued The material of object and be possible without and give full play to antistatic property.If the structural unit from the monomer with polyalkylene oxide chain Containing ratio is 20 mass % or more, then will not give full play to high-rate release property sometimes because of the material of adherend.From above-mentioned viewpoint Consider, as the containing ratio of the structural unit from the monomer with polyalkylene oxide chain, the preferably 2 mass % of mass %~18, more It is preferred that 3 mass of mass %~15 %, the further preferred 3 mass mass of %~10 %.
Specific (methyl) acrylic acid series polymeric compounds contain the structural unit from the monomer with acidic-group.
As the monomer with acidic-group, for example, (methyl) acrylic acid, (methyl) acrylic acid carboxy ethyl can be enumerated Ester, (methyl) acrylic acid carboxy pentyl ester, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) propylene Acryloxypropylethoxysilane hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, ω-carboxyl-polycaprolactone Single (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl fumaric acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid and 2- (methyl) acryloyl-oxyethyl phthalic acid institute (methyl) acrylate with carboxyl represented etc. has the monomer of carboxyl, 2- (methyl) acryloyl-oxyethyl acid phosphorus With the monomer of phosphate representated by acid esters.
As the structural unit from the monomer with acidic-group, it is preferred from the structure list of the monomer with carboxyl Member.There is the structural unit of the monomer of carboxyl can be independent a kind or contain two or more.
As the structural unit from (methyl) acrylate with carboxyl, the preferably structure of the following general formula (1) expression Unit.If carboxyl is bonded via L with (methyl) acrylic acid with the structural unit that general formula (1) indicates, so as to will be high Bonding force when speed removing inhibits lower.More specifically, short with (methyl) acrylic acid etc. from the viewpoint of steric hindrance The monomer with carboxyl of chain is compared, and the reactivity for the monomer and aftermentioned crosslinking agent with carboxyl that general formula (1) indicates is substantially It improves.
In the structural unit that above-mentioned general formula (1) indicates, L is indicated by alkylidene, arlydene, carbonyl and oxygen atom At least one kind of composition divalent linking group, R1Indicate hydrogen atom or methyl.Wherein, when L contains oxygen atom, it is former to form oxygen Group made of son is bonded at least one kind of in alkylidene, arlydene and carbonyl, is bonded with-COO- and-CO-.
Alkylidene in L can be any one of straight-chain, branched and ring-type.Alkylidene in L is straight-chain Or when branched, the carbon atom number of alkylidene preferably 1~12, more preferable 2~10, further preferred 2~6.
As carbon atom number be 1~12 alkylidene, can enumerate methylene, ethylidene, propylidene, butylidene, pentylidene, Hexylidene, heptamethylene, octamethylene, arlydene, decylene, sub-dodecyl etc..
In addition, alcyl (carbocyclic ring) can be enumerated as L when the alkylidene in L is cyclic annular.Cricoid alkylidene can be carbon The carbocyclic ring of atomicity 3~5, as concrete example, preferably cyclohexylidene etc..
The preferred carbon atom number of arlydene in L is 6~10, more preferable phenylene.The bonding position of arlydene is not special Limitation.Such as arlydene be phenylene when, bonding position can be 1 with 4,1 with 2 and 1 with 3 in times One, preferably 1 and 2.
Alkylidene and arlydene in L can have substituent group.As substituent group, the alkane of carbon atom number 1~12 can be enumerated Base, halogen atom, hydroxyl, amino, nitro, phenyl etc..
From the viewpoint of antistatic property and high-rate release property, the linking group by the divalent represented of the L in general formula (1) is excellent The linking group for the divalent for selecting the following general formula (2a) or general formula (2b) to indicate.
In general formula (2a) and (2b), R21~R24Each independently represent the alkylidene or carbon atom of carbon atom number 1~12 The arlydene of number 6~10.N indicates that 0~10 number, m indicate 1~10 number.
R21~R24In alkylidene can be any one of straight-chain, branched and ring-type, preferably straight-chain or Branched, more preferable straight-chain.
R21~R24In the bonding position of arlydene be not particularly limited.For example, arlydene be phenylene when or ring-type Alkylidene when being, for example, cyclohexylidene, bonding position can be 1 and 4,1 with 2 and 1 with 3 in any Kind, preferably 1 and 2.
R21And R22In alkylidene separately preferred carbon atom number be 2~10, more preferable carbon atom number be 2~6. As R21And R22In alkylidene, methylene, ethylidene, propylidene, butylidene, cyclohexylidene etc. can be enumerated.R21And R22In Alkylidene can be the same or different.
R21And R22In arlydene separately preferred phenylene or naphthylene, more preferable phenylene.
R from the viewpoint of antistatic property and high-rate release property, in general formula (2a)21And R22Separately preferred carbon The alkylidene of atomicity 1~12, the alkylidene of more preferable carbon atom number 2~6, the straight-chain of further preferred carbon atom number 2~6 Or the alkylidene of branched.
In general formula (2a), n indicates 0~10 number.Specific (methyl) acrylic acid series polymeric compounds only contain a kind of general formula (1) table When the structural unit shown, n is integer, and when containing two or more, n is the rational as average value.N preferably 0~4, more preferable 0 ~2.
In general formula (2b), R23In the preferred carbon atom number 1~12 of alkylidene alkylidene, more preferable carbon atom number 2~6 Alkylidene, the alkylidene of further preferred carbon atom number 2~4.As R23In alkylidene, methylene, ethylidene, Asia can be enumerated Propyl, butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, decylene, sub-dodecyl etc..
In general formula (2b), R24In the preferred carbon atom number 2~6 of alkylidene straight-chain or branched alkylidene, carbon The cyclic alkylidene (carbocyclic ring of divalent) of atomicity 4~8 or the arlydene of carbon atom number 6~10, more preferable carbon atom number 2~ The cyclic alkylidene or phenylene of the alkylidene of 4 straight-chain or branched, carbon atom number 5~6, further preferred carbon are former The straight-chain of subnumber 2~4 or alkylidene, cyclohexylidene or the phenylene of branched.
In general formula (2b), m indicates 1~10 number.Specific (methyl) acrylic acid series polymeric compounds contain only a kind of general formula (1) and indicate Structural unit when, m is integer, and when containing two or more, m is rational as average value.M preferably 1~4, more preferable 1~ 2。
The structural unit that general formula (1) indicates for example can be specific by the monomer and composition that indicate the following general formula (1a) The other monomers of (methyl) acrylic acid series polymeric compounds are copolymerized together and imported into specific (methyl) acrylic acid series polymeric compounds.
In general formula (1a), R1With L respectively with the R in general formula (1)1It is identical with L meaning.
The monomer that general formula (1a) indicates can use conventional method manufacture, can also suitably select from commercially available monomer It selects.The monomer that the L in monomer indicated as general formula (1a) is indicated by general formula (2a), such as (methyl) acrylic acid dimerization can be enumerated Body (average value of the n in preferred formula (2a) is about 0.4) and ω-carboxyl-polycaprolactone list (methyl) acrylate are (excellent The average value of n in gating formula (2a) is about 1.0).
As these monomers, it is, for example, possible to use as " ARONIX M-5600 " and " ARONIX M-5300 " (with On, Toagosei Co., Ltd's system, trade name) commercially available commercially available product.
In addition, the monomer that L is indicated by general formula (2b) in the monomer indicated as general formula (1a), for example, 2- (first can be enumerated Base) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl fumaric acid, 2- (methyl) acryloyl-oxyethyl Hexahydrophthalic acid and 2- (methyl) acryloyl-oxyethyl phthalic acid.As these monomers, for example, can make With " LIGHT ESTER HO-MS ", " LIGHT ACRYLATE HOA-MS (N) ", " LIGHT ACRYLATE HOA-HH (N) " and " LIGHT ACRYLATE HOA-MPL (N) " (more than, Kyoeisha Chemical Co., Ltd.'s system, trade name) is used as city The commercially available product sold.
The quality of entire infrastructure unit relative to specific (methyl) acrylic acid series polymeric compounds, the structure that general formula (1) indicates The containing ratio of unit preferably 4 mass of mass %~30 %, the more preferable 5 mass mass of %~20 %, further preferred 8 mass %~ 15 mass %.
If the containing ratio for the structural unit that general formula (1) indicates is 4 mass % or more, bonding force when high speed is removed has It is suppressed lower trend.If general formula (1) indicate structural unit containing ratio be 30 mass % hereinafter, if having inhibition by Bonding force caused by the material of adherend reduces and the trend of excellent antistatic property.
Specific (methyl) acrylic acid series polymeric compounds preferably in addition to the structural unit from the monomer with polyalkylene oxide chain with And the structural unit with acidic-group, also contain at least one kind of structural unit from (methyl) alkyl acrylate.
As (methyl) alkyl acrylate, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid Positive nonyl ester, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) acrylic acid n-dodecane base ester, (methyl) The different myristin of acrylic acid, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobomyl acrylate Ester.The alkyl of (methyl) alkyl acrylate can be any one of straight chain, branch or ring-type.
Structural unit from (methyl) alkyl acrylate can be independent a kind or contain two or more.
From the viewpoint of being easily adjusted the bonding force suitable for protective film, as (methyl) alkyl acrylate, preferably make Glass transition temperature when at homopolymer is -30 DEG C of (methyl) alkyl acrylates below.
The glass transition temperature of homopolymer obtains as follows: using differential scanning calorimetry measurement device to the homopolymer (DSC) (Seiko Instruments Inc system, EXSTAR6000) measures sample 10mg, in stream of nitrogen gas with the speed that heats up The condition of 10 DEG C/min of degree is measured, using the inflection point of obtained DSC curve as the glass transition temperature of homopolymer.
It is -30 DEG C of (methyl) alkyl acrylates below, example as glass transition temperature when homopolymer is made Such as, can enumerate n-butyl acrylate (- 57 DEG C), 2- ethylhexyl (- 76 DEG C), methacrylic acid n-dodecane base ester (- 65 DEG C), acrylic acid n-octyl ester (- 65 DEG C), Isooctyl acrylate monomer (- 58 DEG C), the different nonyl ester (- 58 DEG C) of acrylic acid, acrylic acid Different nutmeg base ester (- 56 DEG C) and 2- acryloyl-oxyethyl-succinic acid (- 40 DEG C).
Wherein, from the viewpoint of being easily adjusted the bonding force suitable for protective film, as vitrifying when being made homopolymer Transition temperature is -30 DEG C of (methyl) alkyl acrylates below, is preferably selected from n-butyl acrylate and acrylic acid 2- second At least one party in the own ester of base.
Specific (methyl) acrylic acid series polymeric compounds contain the structural unit from (methyl) alkyl acrylate and (are preferred from Glass transition temperature when homopolymer is made is the structural unit of -30 DEG C of (methyl) alkyl acrylates below) when, phase For the quality of entire infrastructure unit, the structural unit from (methyl) alkyl acrylate is (from when being preferably made homopolymer Glass transition temperature be -30 DEG C of (methyl) alkyl acrylates below structural unit) total containing ratio preferably 65 matter Measure the mass of %~99 %, the more preferable 75 mass mass of %~97 %, the further preferred 80 mass mass of %~95 %.If come from Total containing ratio of the structural unit of (methyl) alkyl acrylate is 65 mass % or more, then close nature (wetability) has change more Excellent trend.In addition, if from (methyl) alkyl acrylate structural unit total containing ratio be 99 mass % hereinafter, Bonding force when then having high speed to remove will not become excessively high, the superior trend of high-rate release property.
Specific (methyl) acrylic acid series polymeric compounds in addition to from the monomer with polyalkylene oxide chain structural unit, have acid Property group structural unit and from (methyl) alkyl acrylate structural unit other than, other structures list can also be contained Member.As the monomer that can form other structures unit, if can with polyalkylene oxide chain monomer, by with acidic-group Structural unit and from (methyl) alkyl acrylate structural unit indicate monomer copolymerization, be just not particularly limited, can To be properly selected according to purpose.
As the monomer that can form other structures unit, for example, (methyl) acrylic acid 2- hydroxy methacrylate, (first can be enumerated Base) representated by acrylic acid 4- hydroxybutyl with (methyl) acrylic monomer of hydroxyl, Phenoxyethyl (methyl) propylene With (methyl) acrylic monomer of aromatic ring, (methyl) acrylic acid representated by acid esters, (methyl) benzyl acrylate With (methyl) acrylic monomer of nitrogen-atoms, benzene representated by amino ethyl ester, (methyl) acrylate Aromatic mono-vinyl base monomer representated by ethylene, α-methylstyrene, vinyl representated by acrylonitrile, methacrylonitrile Cyanogen monomer, vinyl formate, vinyl acetate, vinyl carboxylates monomer representated by vinyl propionate.
The acid value of specific (methyl) acrylic acid series polymeric compounds is 9mgKOH/g~65mgKOH/g.If specific (methyl) third The acid value of olefin(e) acid based polymer is more than 65mgKOH/g, then by binder composition cross-links when forming adhesive phase, formation is glued Mixture layer becomes really up to the mark, and the bonding force of adhesive phase is lower, and during needing to protect adherend, protective film may be from adherend Surface fall off.In addition, having the tendency that antistatic property is easily reduced.If the acid value of specific (methyl) acrylic acid series polymeric compounds is small In 9mgKOH/g, then adhesive phase is excessively soft, and bonding force is easy to get higher, and high speed has the tendency that being difficult to remove when removing.From into From the viewpoint of one step improves high-rate release property, as the acid value of specific (methyl) acrylic acid series polymeric compounds, preferably 9mgKOH/g ~50mgKOH/g, more preferable 9mgKOH/g~35mgKOH/g, further preferred 16mgKOH/g~25mgKOH/g.
Specific (methyl) acrylic acid series polymeric compounds or the acid value of aftermentioned (methyl) acrylic oligomers respectively by with Under calculating formula find out.
Acid value (mgKOH/g)={ (A/100) ÷ B } × 56.1 × 1000 × C
In whole monomer used in specific (methyl) acrylic acid series polymeric compounds of A=or (methyl) acrylic oligomers The monomer with acidic-group containing ratio (quality %)
There is acidic groups used in specific (methyl) acrylic acid series polymeric compounds of B=or (methyl) acrylic oligomers The molecular weight of the monomer of group
Number of the C=with the acidic-group contained in 1 molecule of monomer of acidic-group
It should be noted that 56.1 be the molecular weight of KOH.
Additionally, there are when a variety of monomers with acidic-group, for each monomer, the value found out by above-mentioned formula can be closed It counts and finds out acid value.
The weight average molecular weight (Mw) of specific (methyl) acrylic acid series polymeric compounds is not particularly limited.As specific (methyl) third The weight average molecular weight (Mw) of olefin(e) acid based polymer, preferably 100,000~1,000,000, more preferable 100,000~600,000, further preferred 100,000 ~40 ten thousand.If the weight average molecular weight (Mw) of specific (methyl) acrylic acid series polymeric compounds is 100,000 or more, can be more effectively Inhibit specific (methyl) acrylic acid series polymeric compounds when high speed removing to remain on adherend, there is the dirt further decreased to adherend The trend of dye.In addition, if the weight average molecular weight (Mw) of specific (methyl) acrylic acid series polymeric compounds be 1,000,000 hereinafter, if having parent The superior trend of close property (wetability).
It should be noted that specific (methyl) acrylic acid series polymeric compounds or the weight of aftermentioned (methyl) acrylic oligomers are equal Molecular weight (Mw) is the value measured according to following (1)~(3).
(1) by the solution coating of specific (methyl) acrylic acid series polymeric compounds or (methyl) acrylic oligomers in removing Paper, it is 2 minutes dry at 100 DEG C, it is oligomeric to obtain membranaceous specific (methyl) acrylic acid series polymeric compounds or (methyl) acrylic acid series Object.
(2) using specific (methyl) acrylic acid series polymeric compounds or (methyl) acrylic acid membranaceous obtained in above-mentioned (1) It is oligomer and tetrahydrofuran, obtains the sample solution that solid component concentration is 0.2 mass %.
(3) following conditions are pressed, are measured specific using gel permeation chromatography (GPC) as standard polystyren scaled value The weight average molecular weight (Mw) of (methyl) acrylic acid series polymeric compounds or (methyl) acrylic oligomers.
(condition)
GPC:HLC-8220GPC (Tosoh Co. Ltd. system)
Column: 4 TSK-GEL GMHXL are used
Mobile phase solvent: tetrahydrofuran
Flow velocity: 0.6mL/ minutes
Column temperature: 40 DEG C
The containing ratio of specific (methyl) acrylic acid series polymeric compounds in adhesive composition can suitably be selected according to purpose It selects.The containing ratio of specific (methyl) acrylic acid series polymeric compounds preferably 80 matter in the solid component gross mass of adhesive composition Measure the mass of %~99 %, the more preferable 85 mass mass of %~99 %, the further preferred 90 mass mass of %~98 %.It should say Bright, solid component gross mass means from the total matter for removing residue obtained by the volatile components such as solvent in adhesive composition Amount.
The manufacturing method of specific (methyl) acrylic acid series polymeric compounds is not particularly limited.For example, polymerisation in solution, cream can be used The representative well known polymerization of liquid polymerization, suspension polymerisation and blocky polymerization manufactures monomer polymerization.These polymerization sides It is fairly simple from processing method in method, and from the aspect of capable of being carried out with the short time, preferably polymerisation in solution.
In general, polymerisation in solution in polymerization tank by being packed into defined organic solvent, monomer, polymerization initiator, urging Agent and chain-transferring agent as needed, in stream of nitrogen gas or under the reflux of organic solvent, heating reaction while stirring A few houres and carry out.It as above-mentioned polymerization initiator, is not particularly limited, azo compound can be used for example.
It should be noted that the weight average molecular weight (Mw) and number-average molecular weight (Mn) of (methyl) acrylic acid series polymeric compounds can pass through Reaction temperature, reaction time, organic solvent amount, the type of catalyst or amount are adjusted, so as to adjust at desired molecular weight.
[(methyl) acrylic oligomers]
The adhesive composition of one embodiment of the present invention preferably comprises the (first that weight average molecular weight is 3000~20000 Base) acrylic oligomers.
(methyl) acrylic oligomers are further included by adhesive composition, are able to suppress containing for antistatic agent Amount.In addition, when adhesive composition includes aftermentioned organic silicon modified by polyether, it is low by further including (methyl) acrylic acid series Polymers has the tendency that the content for being able to suppress organic silicon modified by polyether.Adhesive phase when removing protective film from adherend as a result, A part is not easy to remain on adherend, has the tendency that inhibiting the generation of the pollution to adherend.Also, has and inhibit specific (methyl) The compatibility of acrylic acid series polymeric compounds reduces and the trend of the gonorrhoea of generation.
From the viewpoint of inhibiting the generation to the pollution of adherend, (methyl) acrylic oligomers, which preferably comprise, to be come from The structural unit of monomer with carboxyl.The type of monomer with carboxyl is not particularly limited.
As the structural unit from the monomer with carboxyl, specific (methyl) acrylic polymeric described can be enumerated The structural unit from the monomer with carboxyl in object.As the structural unit from the monomer with carboxyl, it is preferred from The structural unit of (methyl) acrylic acid.
From the viewpoint of further decreasing the pollution to adherend, relative to the quality of entire infrastructure unit, (methyl) The containing ratio of the structural unit from the monomer with carboxyl in acrylic oligomers preferably 0.1 matter of mass %~10 Measure %, the more preferable 0.5 mass mass of %~7.0 %, the further preferred 1.0 mass mass of %~5.0 %.
(methyl) acrylic oligomers preferably comprise the structural unit from (methyl) alkyl acrylate.Pass through (first Base) acrylic oligomers contain the structural unit from (methyl) alkyl acrylate, and the adjustment of bonding force becomes easy.
As (methyl) alkyl acrylate, (the first in specific (methyl) acrylic acid series polymeric compounds described can be enumerated Base) alkyl acrylate.
As (methyl) alkyl acrylate contained in (methyl) acrylic oligomers, even if from adhesive phase is sudden and violent From the aspect of also playing high durability when being exposed under hot and humid environment, preferred (methyl) acrylic acid of carbon atom number 4~12 Arrcostab, more preferably (methyl) alkyl acrylate of the carbon atom number 4~12 with branch, further preferred methacrylic acid 2- ethylhexyl.
As containing for the structural unit for coming from (methyl) alkyl acrylate contained in (methyl) acrylic oligomers There is rate, from the viewpoint of durability, quality preferably 65 mass % of mass %~99 relative to entire infrastructure unit, more preferably 75 mass of mass %~95 %, the further preferred 80 mass mass of %~90 %.
(methyl) acrylic oligomers preferably comprise the structural unit from the monomer with polyalkylene oxide chain.As tool Have the monomer of polyalkylene oxide chain, can enumerate in specific (methyl) acrylic acid series polymeric compounds described with polyalkylene oxide chain Monomer.
When (methyl) acrylic oligomers are contained from the structural unit of the monomer with polyalkylene oxide chain, as polycyclic The average addition molal quantity of alkylene oxide unit in oxygen alkane chain, preferably 2 moles~25 moles, no matter from the material of adherend Also from the viewpoint of sufficient antistatic effect capable of being obtained, more preferable 9 moles~23 moles.It should be noted that average addition mole Number is identical as the average addition molal quantity meaning of polyalkylene oxide chain in specific (methyl) acrylic acid series polymeric compounds described.
Relative to the quality of entire infrastructure unit, in (methyl) acrylic oligomers from polyalkylene oxide chain The containing ratio of the structural unit of monomer preferably 5 mass of mass %~30 %, the more preferable 5 mass mass of %~20 %, particularly preferred 5 The mass of quality %~15 %.
If the containing ratio of the structural unit from the monomer with polyalkylene oxide chain be 5 mass % or more, have resist it is quiet Electrically superior trend.In addition, if the containing ratio of the structural unit from the monomer with polyalkylene oxide chain is 30 matter Amount % can be further decreased to adherend hereinafter, do not polymerize after polymerization reaction then and the content of monomer of remaining is inhibited Pollution.
(methyl) acrylic oligomers are in the range of playing one embodiment of the present invention resulting effect, except coming from The structural unit of monomer with carboxyl, from (methyl) alkyl acrylate structural unit and from have polyalkylene oxide Other than the structural unit of the monomer of chain, other structures unit can also be contained.
At this moment, shared in the entire infrastructure unit of (methyl) acrylic oligomers, from the monomer with carboxyl Structural unit, the structural unit from (methyl) alkyl acrylate and structure list from the monomer with polyalkylene oxide chain Total containing ratio of member, quality preferably 80 mass % or more, more preferable 90 mass % or more relative to entire infrastructure unit, Further preferred 95 mass % or more.
As the monomer that can form other structures unit, for example, (methyl) acrylic acid 2- hydroxy methacrylate, (first can be enumerated Base) representated by acrylic acid 4- hydroxybutyl with (methyl) acrylic monomer of hydroxyl, (methyl) acrylic acid phenoxy group second With (methyl) acrylic monomer of aromatic ring, amino-ethyl (methyl) representated by ester, (methyl) benzyl acrylate With (methyl) acrylic monomer of nitrogen-atoms, benzene representated by acrylate, (methyl) acrylate Aromatic mono-vinyl base monomer representated by ethylene, α-methylstyrene, vinyl representated by acrylonitrile, methacrylonitrile Cyanogen monomer, vinyl formate, vinyl acetate, vinyl carboxylates monomer representated by vinyl propionate.
When the adhesive composition of one embodiment of the present invention includes (methyl) acrylic oligomers, (methyl) propylene Acid system oligomer can be independent a kind, be also possible to two or more different such as composition, the weight average molecular weight of monomer.
Relative to specific 100 mass parts of (methyl) acrylic acid series polymeric compounds, the content of (methyl) acrylic oligomers is excellent Select 0.05 mass parts~5.00 mass parts.If the content of (methyl) acrylic oligomers is 0.05 mass parts or more, high Bonding force when speed removing will not become excessively high, have the tendency that high-rate release property is excellent.(if methyl) acrylic oligomers Content be that 5.00 below the mass, then during needing to protect adherend, protective film can be prevented de- from the surface of adherend It falls, also, has the superior trend of high-rate release property.Consider from above-mentioned viewpoint, as containing for (methyl) acrylic oligomers Amount, more preferable 0.10 mass parts~3.00 mass parts, further preferred 0.10 mass parts~2.50 mass parts.
The acid value preferred 10mgKOH/g~200mgKOH/g, more preferable 15mgKOH/g of (methyl) acrylic oligomers~ 100mgKOH/g, further preferred 15mgKOH/g~50mgKOH/g.
If the acid value of (methyl) acrylic oligomers is 10mgKOH/g or more, specific (methyl) propylene can be made Sour based polymer and aftermentioned crosslinking agent are full cross-linked, in addition, having the tendency that further increasing high-rate release property.(if methyl) The acid value of acrylic oligomers is 200mgKOH/g hereinafter, then having the tendency that keeping antistatic property better.
It should be noted that the calculation method of the acid value of (methyl) acrylic oligomers is as described above.
It is preferred that the weight average molecular weight of (methyl) acrylic oligomers is 3000~20000.(if methyl) acrylic acid series The weight average molecular weight of oligomer is 3000 or more, then having can prevent (methyl) acrylic oligomers from remaining on becoming for adherend Gesture.In addition, if the weight average molecular weight of (methyl) acrylic oligomers be 20000 hereinafter, if can reduce adhesive phase Mist degree trend.Consider from above-mentioned viewpoint, as the weight average molecular weight of (methyl) acrylic oligomers, preferably 4000~ 15000, more preferable 5000~10000.
It is surveyed in the same manner as the measuring method of the weight average molecular weight (Mw) of specific (methyl) acrylic acid series polymeric compounds described The weight average molecular weight (Mw) of fixed (methyl) acrylic oligomers.
< crosslinking agent >
The adhesive composition of one embodiment of the present invention includes at least one kind of crosslinking agent.It, can by the inclusion of crosslinking agent It is reacted with acidic-group representated by the carboxyl in specific (methyl) acrylic acid series polymeric compounds and forms cross-linked structure.As crosslinking Agent, as long as being capable of specific (methyl) acrylic acid series polymeric compounds contained in the adhesive composition with one embodiment of the present invention In acidic-group reaction and form cross-linked structure, be just not particularly limited, for example, epoxide, isocyanates can be enumerated Compound, aziridine cpd, metallo-chelate.From compared with the situation for using isocyanate compound, epoxide etc., Cross-linking reaction is fast, further, it is possible to from the viewpoint of shortening the curing end time, as crosslinking agent, preferably metallo-chelate.
As metallo-chelate, the metallo-chelate of polyvalent metal atom Yu organic compound coordination bonding can be enumerated.Make For polyvalent metal atom, for example, can enumerate Al, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn and Ti.Wherein, from the viewpoint of low cost and obtained easiness, preferably Al, Zr and Ti, more preferable Al.
As the atom in the organic compound of polyvalent metal atom coordination bonding, oxygen atom etc. can be enumerated.As organic Compound can enumerate Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, ketone compound etc..
It, can be particularly preferably using the praseodynium aluminium etc. readily and stably operated as metallo-chelate.In addition, golden Belonging to chelate can be independent a kind or is used in combination of two or more.
As the equivalent of crosslinking agent, relative to 1 equivalent of acidic-group of specific (methyl) acrylic acid series polymeric compounds, preferably 0.3 equivalent~2.0 equivalents, more preferable 0.4 equivalent~1.5 equivalents, further preferred 0.6 equivalent~1.2 equivalents.
If the content of crosslinking agent be 0.3 equivalent more than, have by high speed remove when bonding force inhibit it is lower become Gesture, if the content of crosslinking agent be 2.0 equivalents hereinafter, if having can to adhesive phase assign protective film will not from adherend accident The trend of the bonding force of the degree of ground removing.
The equivalent of crosslinking agent is the value calculated by formula below.
Equivalent=(A × B/C)/(D1×E1/F1+D2×E2/F2+····+Dn×En×Fn)
The valence mumber of the metal of A=crosslinking agent
The mass fraction (amount as solid component) of B=crosslinking agent
The molecular weight of C=crosslinking agent
D1、D2、···DnThere is acidic groups in whole monomer used in=specific (methyl) acrylic acid series polymeric compounds The containing ratio (quality %) of each monomer of group
E1、E2、···EnThe number of the acidic-group contained in 1 molecule of=each monomer with acidic-group
F1、F2、···FnEach monomer used in=specific (methyl) acrylic acid series polymeric compounds with acidic-group Molecular weight
It should be noted that n indicates the species number of the monomer used, for example, (methyl) acrylic monomer used is a kind When, it calculates and D is used only1, do not use D2···Dn。
< antistatic agent >
The adhesive composition of one embodiment of the present invention contains at least one kind of antistatic agent.
As antistatic agent, the ionic compound of alkali metal salt, organic salt etc. can be enumerated.As antistatic agent, from from Sub- dissociative is high, even if from the aspect of a small amount of antistatic property excellent using also easy embodiment, preferred as alkali salt and organic salt.
As long as alkali metal salt is with lithium ion (Li+), sodium ion (Na+), potassium ion (K+), rubidium (Rb+) etc. to be cationic Metal salt is just not particularly limited.
As the combination of alkali metal salt, for example, it is preferable to using by being selected from Li+、Na+And K+In at least one kind of cation Be selected from Cl?、Br?、I?、BF4 ?、PF6 ?、SCN?、ClO4 ?、CF3SO3 ?、(FSO2)2N?、(CF3SO2)2N?、(C2F5SO2)2N?With And (CF3SO2)3C?In the metal salt that constitutes of at least one kind of anion.
Wherein, as alkali metal salt, from the viewpoint of antistatic property, LiBr, LiI, LiBF are preferably selected from4、LiPF6、 LiSCN、LiClO4、LiCF3SO3、Li(FSO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N and Li (CF3SO2)3In C extremely Few a kind of lithium salts, is more preferably selected from LiClO4、LiCF3SO3, Li (CF3SO2)2N、Li(C2F5SO2)2N and Li (CF3SO2)3C In at least one kind of lithium salts.These alkali metal salts can be independent a kind or be used in combination of two or more.
Organic salt preferably comprises organic cation and its counter ion counterionsl gegenions.
As the fusing point of organic salt, preferably 30 DEG C or more.If the fusing point of organic salt is 30 DEG C or more, to adherend Migration is few, has the tendency that being able to suppress pollution, thus preferably.
As organic cation, for example, imidazoles can be enumeratedCation, pyridineCation, alkyl pyrrolidineSun Ion, the ammonium cation as substituent group with organic group, sulfonium cation and work as substituent group with organic group There is organic group for substituent groupCation.Wherein, as organic cation, from the viewpoint of antistatic property, preferably Selected from pyridineCation and imidazolesIt is at least one kind of in cation.
The anion of counter ion counterionsl gegenions as organic cation is not particularly limited, inorganic anion or organic anion ?.Wherein, the anion part as the counter ion counterionsl gegenions for becoming organic cation, it is excellent especially because antistatic property is more excellent Select the fluo anion containing fluorine atom, hexafluorophosphoric acid salt anionic (PF6 ?) more preferably.
As organic salt, pyridine is preferably enumeratedSalt, imidazolesSalt, alkylammonium salt, alkyl pyrrolidineSalt, alkyl Salt etc..Wherein, as organic salt, it is preferably selected from pyridineSalt and imidazolesIt is at least one kind of in salt, more preferable pyridineSun from Son or imidazolesThe salt of cation and fluo anion.
Relative to specific 100 mass parts of (methyl) acrylic acid series polymeric compounds, the content of antistatic agent preferably 0.05 mass parts ~1.50 mass parts, more preferable 0.10 mass parts~1.00 mass parts.Relative to specific 100 matter of (methyl) acrylic acid series polymeric compounds Part is measured, the content of antistatic agent is 0.05 mass parts or more, then has the superior trend of antistatic property.The content of antistatic agent is 1.50 below the mass, then has the efficiency of the antistatic effect of the content relative to antistatic agent to be easy to become higher trend.
[organic silicon modified by polyether]
The adhesive composition of one embodiment of the present invention preferably comprises at least one kind of organic silicon modified by polyether.In addition, because There is reactive group for organic silicon modified by polyether, so bonding film, which can more easily be removed and be had from adherend, can obtain pair The trend of the few bonding film of the pollution of adherend.
By specific (methyl) acrylic polymeric of organic silicon modified by polyether and the structural unit indicated with general formula (1) When object, antistatic agent and crosslinking agent are used together, antistatic property can be more effectively embodied.
When organic silicon modified by polyether has the hydroxyl of polyether-based and polyether-based end, there is the superior antistatic property of display, Effectively inhibit the trend of the pollution to adherend.Especially because the intramolecular in organic silicon modified by polyether has end for hydroxyl The polyalkylene oxide chain of base, so in the presence of antistatic property trend is effectively played.Because organic silicon modified by polyether is tended in carrying out self-adhesion Near the surface of the adhesive phase of mixture composite, so with the presence of the polyalkylene oxide chain locality to interact with alkali metal salt Trend near the surface of adhesive phase.Speculate that its result reduces the surface resistance value on the surface of adhesive phase.By simultaneously With organic silicon modified by polyether, has the tendency that the amount for the antistatic agent being able to suppress in adhesive composition.
From the viewpoint of further decrease antistatic property and to the pollution of adherend, organic silicon modified by polyether preferably comprises Structural unit from dialkylsiloxane and the structural unit from alkyl (hydroxyl polyalkylene oxygroup alkyl) siloxanes Polysiloxane compound.
The carbon atom number of alkyl in dialkylsiloxane preferably 1~4, more preferable 1.
In addition, the carbon atom number preferably 2 of the polyalkylene oxide chain in alkyl (hydroxyl polyalkylene oxygroup alkyl) siloxanes~ 4, more preferable 2~3.The carbon atom number of polyalkylene oxide chain in alkyl (hydroxyl polyalkylene oxygroup alkyl) siloxanes contains number It is preferred that 1~100, more preferable 10~100.The carbon atom number of alkyl in alkyl (hydroxyl polyalkylene oxygroup alkyl) siloxanes is excellent Select 1~4.
Organic silicon modified by polyether contains the structural unit from dialkylsiloxane and comes from alkyl (hydroxyl polyalkylene oxide Base alkyl) siloxanes structural unit when, the structural unit from dialkylsiloxane containing number preferably 100 hereinafter, more excellent Select 1~80.In addition, from alkyl (hydroxyl polyalkylene oxygroup alkyl) siloxanes structural unit containing number preferably 2~ 100, more preferable 2~80.
Consider that organic silicon modified by polyether is excellent from adhesiveness, antistatic property and the pollution viewpoint further decreased to adherend The polysiloxane compound for selecting the following general formula (3) to indicate.
In general formula (3), p is the repeat number of dimethyl siloxane structural unit, indicates 0~100 number.Q is with polycyclic The repeat number of the methyl propylene siloxane structural unit of oxidative ethane chain indicates 2~100 number.In addition, a is ethylene oxide knot The repeat number of structure unit indicates 1~100 number.Here, when the compound that general formula (3) indicates is the aggregate of multiple compounds, P, q and a is the average value of the aggregate of compound, is rational.
The number that the repeat number a of ethylene oxide structure unit is 1~100, preferably 10~100 number.If a is 1 or more, Sufficient electric conductivity is obtained, the trend of antistatic property is further increased.In addition, if a be 100 hereinafter, if having with constitute it is viscous The compatibility of the other compositions of mixture composite improves, the trend that the transparency of adhesive phase further increases.
In addition, the number that the repeat number p of dimethyl siloxane structural unit is 0~100, preferably 1~80 number.Also, first The number that the repeat number q of base propylidene siloxane structural unit is 2~100, preferably 2~80 number.If q is 2 or more, have The trend further increased to sufficient electric conductivity, antistatic property.In addition, if q be 100 hereinafter, if with constitute adhesive group The compatibility for closing the other compositions of object improves, and has the tendency that the transparency of adhesive phase improves.
The weight average molecular weight of organic silicon modified by polyether is not particularly limited, for example, can be 5000~20000, preferably 6000~15000.
In addition, the HLB value of organic silicon modified by polyether is not particularly limited.As HLB value, from the compatibility with resin, table From the viewpoint of tending to property of face and adhesiveness, preferably 5~16, more preferable 7~15.
HLB value is the scale for indicating the hydrophily and hydrophobic balance of organic silicon modified by polyether.In this specification, HLB Value according to the Griffin method calculated by following formula definition, but organic silicon modified by polyether be commercially available product when, preferentially use its catalogue Data.
HLB={ (summation of the formula weight of hydrophily base portion point)/(molecular weight of organic silicon modified by polyether) } × 20
Organic silicon modified by polyether has dimethyl siloxane structural unit and the first with polyethylene oxide chain in the molecule Base propylidene siloxane structural unit.These structural units can respectively constitute block copolymer, also may be constructed random copolymerization Close object.
As the concrete example for the organic silicon modified by polyether that general formula (3) indicate, for example, " SF-8428 ", " FZ- can be enumerated 2162 " and " SH-3773M " (more than, TorayDow Corning Co. Ltd. system).
Organic silicon modified by polyether can be selected from above-mentioned commercially available product.In addition, organic silicon modified by polyether can be by making to have There is the organic compound of unsaturated bond and polyethylene oxide chain to be grafted on the dimethyl with silane by silicon hydrogenation to gather It is obtained on siloxane main chain.
Relative to specific 100 mass parts of (methyl) acrylic acid series polymeric compounds, the content of organic silicon modified by polyether preferably 0.05 Mass parts~1.00 mass parts, more preferable 0.05 mass parts~0.70 mass parts, further preferred 0.05 mass parts~0.30 matter Measure part.
If the content of organic silicon modified by polyether is 0.05 mass parts or more, there is the superior trend of antistatic property.Separately Outside, if the content of organic silicon modified by polyether is 1.00 below the mass, to inhibit the generation of the pollution (mist) to adherend, separately Outside, having the tendency that being able to suppress reduces with the compatibility of specific (methyl) acrylic acid series polymeric compounds and generates gonorrhoea.
Adhesive composition may include the polysiloxane compound of general formula (3) expression and have different from general formula (3) The dimethyl polysiloxane compound containing polyethyleneoxy of structure.
As with the structure different from general formula (3) the dimethyl polysiloxane compound containing polyethylene oxide chain, For example, the end that polyethylene oxide chain can be enumerated be alkoxy, the compound of acyloxy and not in side chain and in main chain or Contain the compound of polyethylene oxide chain in end.
As the dimethyl polysiloxane compound containing polyethylene oxide chain with the structure different from general formula (3) Concrete example, for example, can enumerate " BY-16-201 ", " FZ-77 ", " FZ-2104 ", " FZ-2110 ", " FZ-2203 ", " FZ-2207 ", " FZ-2208 ", " L-7001 ", " L-7002 ", " SF-8427 ", " SH-3749 " and " SH-8400 " (more than, TorayDow Corning Co. Ltd. system).
Adhesive composition includes the poly- silicon of the dimethyl containing polyethylene oxide chain with the structure different from general formula (3) When siloxane compound, as its containing ratio, relative to the gross mass of polysiloxane compound, preferably 0.05 mass % is hereinafter, more It is preferred that 0.03 mass % or less.
[other compositions]
Adhesive composition is in addition to specific (methyl) acrylic acid series polymeric compounds, crosslinking agent, antistatic agent and belongs to any It, as needed, can also be suitably containing weather-proof other than (methyl) acrylic oligomers and organic silicon modified by polyether of ingredient Property stabilizer, tackifier, plasticizer, softening agent, removing auxiliary agent, dyestuff, pigment, inorganic filler, surfactant etc..
" protective film "
The protective film of one embodiment of the present invention has the friendship for the adhesive composition for belonging to an embodiment of the present invention Join the adhesive phase and substrate of object.The protective film of one embodiment of the present invention, which passes through to have, comes from one embodiment of the present invention Adhesive composition adhesive phase, though with adherend material, high-rate release property and antistatic property are all excellent Trend.
As long as adhesive phase can be formed on substrate, substrate used in the protective film of one embodiment of the present invention does not have There is special limitation.
From the viewpoint of the inspection and management for carrying out optical component by perspective, substrate can be enumerated using Polyester tree Rouge, acetic acid esters system resin, polyether sulfone system resin, polycarbonate-based resin, polyamide resin, polyimides system resins, polyene The film of the resins such as hydrocarbon system resin, acrylic resin.Wherein, from the viewpoint of surface protection performance, as substrate, preferably make With the film of polyester based resin, if it is considered that practicability, more preferably uses the film of polyethylene terephthalate (PET) resin.
The thickness of substrate generally can be for 500 μm hereinafter, preferably 5 μm~300 μm, more preferably 10 μm~200 μm.
Antistatic layer can be set in the one side of substrate or two sides.In addition, in the side equipped with adhesive phase of substrate Surface, Corona discharge Treatment can be implemented in order to improve the adaptation with adhesive phase etc..
The adhesive phase of the adhesive composition from one embodiment of the present invention is equipped on substrate.
As the forming method of adhesive phase, for example, can directly or as needed be used using by adhesive composition Solvent appropriate dilution, after being coated on substrate, the dry and method that removes solvent.
Furthermore it is possible to the following method: first by using organic siliconresin etc. implement demoulding processing paper or Coating adhesive composition on the stripping film that the film appropriate of polyester film etc. is constituted, heat drying and form adhesive phase, connect down Come, the adhesive phase side pressure of stripping film is connected to substrate, is transferred to adhesive phase on substrate.
Adhesive phase in one embodiment of the present invention is with specific (methyl) acrylic acid series polymeric compounds of cross-linking agents Made of adhesive phase.Bonding force when thereby, it is possible to remove the high speed of adhesive phase inhibits at lower.
It is not particularly limited with the condition of specific (methyl) acrylic acid series polymeric compounds of cross-linking agents.For example, by 23 DEG C, in the environment of 50%RH, curing dozens of minutes~several days, to terminate the cross-linking reaction of adhesive composition.
The thickness for forming adhesive phase on base material can be according to the table of bonding force, optical component required by protective film Surface roughness etc. is suitably set.As the thickness of adhesive phase, in general, 1 μm~100 μm can be illustrated, preferably 5 μm~ 50 μm, more preferably 10 μm~30 μm or so.
If the bonding force of adhesive phase is got higher, the high speed of large area is difficult to the trend removed from adherend when removing, Therefore as the bonding force (peeling force) under peeling rate 30m/ minutes (high speed is removed), preferably smaller than 2.00N/25mm is more excellent Select 1.00N/25mm or less.
During needing to protect adherend, from the viewpoint of prevent protective film from the viewpoint of falling off the surface of adherend, as Bonding force (peeling force) under peeling rate 30m/ minutes (high speed is removed), preferably greater than 0.15N/25mm, more preferable 0.20N/ 25mm or more.
The purposes of the protective film of one embodiment of the present invention is not particularly limited, for example, of the invention one can be made real The protective film layer for applying mode is stacked in the surface of optical component, protects the surface of optical component not contaminated or damages.In addition, this hair The protective film of a bright embodiment can also fit in the metal plates such as iron, stainless steel (SUS), protect the surface of metal plate not by Pollution or damage.
When protective film is used in optical component, optical component is added with the state that protective film layer is laminated on optical component for punching The each process such as work, inspection, conveying, the assembling of LCD panel implement autoclave process, high temperature ageing processing etc. as needed Pressurized treatments are heated, removes and removes from optical component in the stage for not needing surface protection.
As optical component, can enumerate constitute the components of machines (optical apparatus) such as image display device, input unit or Component used in these machines of person.As the concrete example of optical component, polarizing film, wavelength plate, phase plate, optics can be enumerated Compensation film, brightness improve film, light guide plate, reflectance coating, antireflection film, transparent conductive film (ito film) etc..
[embodiment]
Hereinafter, one embodiment of the present invention is specifically described using embodiment.But it is real that the present invention is not restricted to these Apply example.
(Production Example A-1)
The manufacture-of (methyl) acrylic acid series polymeric compounds (A-1)
Ethyl acetate is added in the reaction vessel for having thermometer, blender, nitrogen ingress pipe and reflux cooler In addition in another container 70.0 mass parts are added as 60.0 mass parts of n-butyl acrylate (BA) of monomer, acrylic acid (monomer that general formula (1a) indicates, East Asia synthesize the meeting of strain formula by 24.9 mass parts of 2- ethylhexyl (2EHA), ARONIX M-5300 Society's system) 10.0 mass parts, methoxy polyethylene glycol acrylate (the average addition molal quantity 9 of alkylene oxide unit) (MePEGA) 5.1 mass parts, are mixed and monomer mixture are made.20.0 mass % in the monomer mixture are added to reaction vessel In, after then the air in reaction vessel is replaced with nitrogen, add as polymerization initiator azodiisobutyronitrile (with Under, also referred to as " AIBN ") 0.01 mass parts, under stirring in nitrogen atmosphere, by the mixture temperature heating in above-mentioned reaction vessel To 85 DEG C, start initial reaction.After initial reaction is basic, remaining 80.0 mass % of monomer mixture is gradually added respectively It is reacted about 2 hours with while the mixture of 15.0 mass parts of ethyl acetate and AIBN0.10 mass parts, then, then reacts 2 Hour.Thereafter, the solution that AIBN0.10 mass parts are dissolved in 25.0 mass parts of ethyl acetate was added drop-wise to 1 hour above-mentioned mixed It closes in object, then reacts 1.5 hours.After reaction, the solution of (methyl) acrylic acid series polymeric compounds (A-1) is obtained.
The solid component of the solution of (methyl) acrylic acid series polymeric compounds (A-1) is 48.0 mass %.(methyl) that will be obtained The acid value and weight average molecular weight (Mw) of acrylic acid series polymeric compounds (A-1) are shown in table 1.
It should be noted that " solid component " refer to from the solution of (methyl) acrylic acid series polymeric compounds remove solvent obtained by it is residual Slag.Acid value and weight average molecular weight (Mw) are found out with the method described.
Acid value calculates as follows.
Acid value (mgKOH/g)={ (A/100) ÷ B } × 56.1 × 1000 × C
Tool in whole monomer used in A=(methyl) acrylic acid series polymeric compounds or (methyl) acrylic oligomers There is a containing ratio (quality %) of the monomer of acidic-group: 10.0
B=has the monomer of the acidic-group of the structural unit as (methyl) acrylic acid series polymeric compounds (A-1) The molecular weight of ARONIX M-5300: 300.4
Number of the C=with the acidic-group contained in 1 molecule of monomer of acidic-group: 1
Acid value={ (10.0/100) ÷ 300.4 } × 56.1 × 1000 × 1=18.7
(Production Example A-2~A-21)
(methyl) acrylic acid series polymeric compounds (A-2)~(A-21) manufacture-
It in Production Example A-1, is changed by monomer component shown in table 1, suitably adjusts polymerization initiator amount etc., remove Other than this, the solution of (methyl) acrylic acid series polymeric compounds (A-2)~(A-21) is manufactured in the same manner as Production Example A-1.It will obtain (methyl) acrylic acid series polymeric compounds acid value and weight average molecular weight (Mw) it is shown in table 1.
It should be noted that acid value and weight average molecular weight (Mw) are found out with the method described.
(Production Example B)
The manufacture-of (methyl) acrylic oligomers (B)
In the reaction vessel for having stirring blade, thermometer, nitrogen ingress pipe, cooler, dropping funel, methyl is added 100.0 mass parts of ethyl ketone, methoxy polyethylene glycol methacrylate-styrene polymer (the average addition molal quantity 23 of alkylene oxide unit) (MePEGMA) 10.0 mass parts are heated to reflux temperature while stirring under nitrogen atmosphere.It is added and is pre-mixed in dropping funel 85.0 mass parts of 2-Ethylhexyl Methacrylate (2EHMA) well, 5.0 mass parts of acrylic acid (AA), methyl ethyl ketone The mixed solution of 100.0 mass parts, 5.0 mass parts of azodiisobutyronitrile, the reaction of reflux temperature was added gradually to 120 minutes In container.Thereafter it maintains to react 240 minutes in the state of reflux temperature, reaction was completed.
The solid component of the solution of obtained (methyl) acrylic oligomers (B) is 33.0 mass %.By (methyl) third The acid value and weight average molecular weight (Mw) of olefin(e) acid system oligomer (B) are shown in table 1.
It should be noted that acid value and weight average molecular weight (Mw) are found out with the method described.
[table 1]
Abbreviation in table 1 is as follows.It should be noted that the "-" in table 1 indicates to be free of the ingredient.
BA: n-butyl acrylate
2EHA: 2-EHA
2HEA: acrylic acid 2- hydroxy methacrylate
2EHMA: 2-Ethylhexyl Methacrylate
2MTA: acrylic acid 2- methoxy acrylate
M-5300: ω-carboxyl-polycaprolactone (n ≒ 2) mono acrylic ester (monomer that general formula (1a) indicates) (commodity Name: ARONIX M-5300, Toagosei Co., Ltd's system)
AA: acrylic acid
HOA-MS:2- acryloyl-oxyethyl-succinic acid (monomer that general formula (1a) indicates) (trade name: LIGHT ACRYLATE HOA-MS (N), Kyoeisha Chemical Co., Ltd.'s system)
MePEGA: methoxy polyethylene glycol acrylate (the average addition molal quantity of alkylene oxide unit be respectively 4 or 9)
MePEGMA: methoxy polyethylene glycol methacrylate-styrene polymer (the average addition molal quantity of alkylene oxide unit is 23)
MePPGA: methoxyl group polypropylene glycol acrylate (the average addition molal quantity of alkylene oxide unit is 2)
1 > of < embodiment
208.3 mass parts are packed into the four-hole boiling flask for having stirring blade, thermometer, cooler, dropping funel (with solid 100 mass parts of body ingredient meter) Production Example A-1 in prepare (methyl) acrylic acid series polymeric compounds (A-1) solution (solid at Point 48.0 mass %), (methyl) acrylic acid for preparing in the Production Example B of 1.2 mass parts (0.40 mass parts in terms of solid component) It is the Li (CF as antistatic agent of the solution (33.0 mass % of solid component) of oligomer (B), 0.150 mass parts3SO2)2N Liquid temperature in flask is maintained at 25 DEG C of progress nearby mixing in 4 hours and stirred by (LiTFSI of Morita Chemical Co., Ltd.) It mixes.SH-3773M (TorayDow Corning Co. Ltd. system, solid of the addition as organic silicon modified by polyether thereto 100.0 mass % of ingredient) 0.100 mass parts, as crosslinking agent by praseodynium aluminium (trade name: Aluminum Chelate A, Kawaken Fine Chemical Co. Ltd. system) it is diluted with acetylacetone,2,4-pentanedione and the aluminium chelate compound of dilution with toluene Object (9.72 mass % of solid component) 25.7 mass parts (2.5 mass parts, 0.69 equivalent in terms of solid component), are sufficiently stirred, obtain To adhesive composition solution.
Using the adhesive composition solution, according to the production method production test protection of test protective film below Film carries out various physical property tests.The obtained results are shown in tables 2.
It should be noted that the equivalent of the praseodynium aluminium (aluminium chelate compound) contained in above-mentioned aluminium chelate compound dilution is opposite The amount of the acidic-group contained in (methyl) acrylic acid series polymeric compounds.
The calculating of the equivalent of aluminium chelate compound is calculated with the method described, specifically following to calculate.
Equivalent=(A × B/C)/(D1×E1/F1+D2×E2/F2+····+Dn×En×Fn)
The valence mumber of the metal of A=aluminium chelate compound: 3.0
The mass fraction (amount in terms of solid component) of B=aluminium chelate compound: 2.5 mass parts
The molecular weight of C=aluminium chelate compound: 324.3
D1Each monomer with acidic-group in whole monomer used in=(methyl) acrylic acid series polymeric compounds contains Have rate (quality %): 10.0 mass %
E1=the number of acidic-group respectively contained in 1 molecule of the monomer with acidic-group: 1
F1The molecular weight of=ARONIX M-5300: 300.4
The type of (methyl) acrylic monomer that n=is used: 1
Equivalent=(A × B/C)/(D1×E1/F13 × 2.5/324.3 of)=()/(10.0 × 1/300.4)=0.69
[evaluation]
(1) the test production of protective film
As substrate, in polyethylene terephthalate (PET) film (trade name: Teijin Tetoron Film Type G2,38 μm of thickness, Teijin DuPont Film Co. Ltd. system) on the coated weight after drying be 20g/m2Side Formula coating adhesive composition solution, it is 60 seconds dry with hot air circulation type drying machine at 100 DEG C.Thereafter, adhesive will be coated with The PET film of composition solution and the mold release film being surface-treated with organic silicon-type release agent (trade name: Film binder 100E-0010NO23,100 μm of thickness, Tengsen Industrial Co., Ltd's system) with the coated face of adhesive composition solution and demoulding The mode of the surface treatment face contact of film is overlapped and laminated body is made.By the laminated body by pressurization roll to crimp pasting It after conjunction, is cured 1 hour under conditions of 23 DEG C, 50%RH, makes test protective film.
The production > of < test specimen 1~4
1 > of < test specimen
The demoulding film stripping that test manufactured in above-mentioned (1) is used to protective film keeps the triacetic acid acid as adherend fine It ties up plain (TAC) film (trade name: Lonza TAC100, PANAC Co. Ltd. system) to be overlapped, by pressurizeing, roll crimp pasting It closes, is cut into the size of 25mm × 150mm, test specimen 1 is made (relative to TAC).
2 > of < test specimen
The demoulding film stripping that test manufactured in above-mentioned (1) is used to protective film, with the PET film (commodity as adherend Name: Co. Ltd. system is spun by COSMOSHINE A-4300, Japan) overlapping, by pressurizeing, roll crimp being bonded, and is cut into Test specimen 2 is made in the size of 25mm × 150mm (relative to PET).
3 > of < test specimen
The demoulding film stripping that test manufactured in above-mentioned (1) is used to protective film, the surface as adherend is applied firmly PET (hereinafter also referred to as " HCPET ") film (trade name: KB Film G01S, Co., Ltd.'s Kimoto system) of processing to be applied firmly The mode that the face of processing is contacted with adhesive phase is overlapped, by pressurize roll crimp being bonded, be cut into 25mm × Test specimen 3 is made in the size of 150mm (relative to HCPET).
4 > of < test specimen
The demoulding film stripping that test manufactured in above-mentioned (1) is used to protective film will carry out after the cold rolling as adherend Stainless steel plate (BASUS) (trade name: SUS304 (BA), P Co., Ltd.'s ALTEK system) weight of bright annealing (non-oxidation tempering) Folded, by pressurizeing, roll crimp being bonded, and is cut into the size of 25mm × 150mm, be made test specimen 4 (relative to BASUS)。
(2) high-rate release property
The test specimen 1~4 prepared among the above is placed 24 hours under conditions of 23 DEG C, 50%RH respectively.Thereafter, make With device shown in FIG. 1, bonding force when 180 ゜ removing is measured under 30m/ minutes high-speed conditions of peeling rate.It is specific and Speech holds examination as shown in Figure 1, test specimen is placed on glass plate in such a way that glass plate is contacted with the surface of adherend The one end for testing sample is pulled along the surface of glass plate in 180 ° of directions, thus removes substrate (PET film) from adhesive phase.
According to evaluation criteria below, high-rate release property is evaluated, the results are shown in table 2.
[evaluation criteria]
AA: the bonding force to whole adherends is 0.20N/25mm~1.00N/25mm, and fissility is very excellent, bonding Power is excellent.
A: the bonding force to whole adherends is more than 0.15N/25mm and is less than 2.00N/25mm, is glued at least one The bonding force of object is more than 0.15N/25mm and is less than 0.20N/25mm, or more than 1.00N/25mm and is less than 2.00N/25mm, Fissility is excellent, and bonding force can be said to be excellent.
B: the bonding force at least one adherend is 2.00N/25mm or more, and fissility is slightly poor, is unallowable model It encloses.
C: the bonding force at least two adherend is 2.00N/25mm or more, and fissility is poor, is unallowable range.
D: the bonding force at least one adherend is 0.15N/25mm hereinafter, causing unexpectedly to take off from the surface of adherend It falls, it is excessively poor, it is as the unallowable range of protective film.
(3) antistatic property
After the test specimen 1~4 prepared among the above is placed 24 hours under conditions of 23 DEG C, 50%RH respectively, with Above-mentioned (2) identical method was removed as shown in Figure 1 in 180 directions ゜ with peeling rate 30m/ minutes (high speed).
With the potential measuring instrument (commodity of fixed configurations (position of the surface 10mm apart from adherend) in defined position Name: KSD-0303, Kasuga Electric K. K.'s system) current potential on the surface of the adherend generated when removing is measured.It should The absolute value of measured value evaluates antistatic property as release band voltage, according to evaluation criteria below, the results are shown in table 2.
[evaluation criteria]
AA: the absolute value of the release band voltage of whole adherends is 0.5kv hereinafter, antistatic property is very excellent.
A: the absolute value of the release band voltage of whole adherends is more than 0.5kv and is 1.0kv hereinafter, antistatic property is excellent It is different.
B: the absolute value of the release band voltage of at least one adherend is more than 1.0kv and is 1.5kv hereinafter, antistatic property is omited Difference is unallowable range.
C: the absolute value of the release band voltage of at least one adherend is more than 1.5kv, and antistatic property is poor, is unallowable Range.
1~8 > of 2~embodiment of < embodiment 23 and comparative example
In embodiment 1, composition is changed to composition shown in table 2, in addition to this, prepares 2 institute of table similarly to Example 1 The adhesive composition shown.Test protective film is made using obtained adhesive composition, uses the test protective film Make test specimen 1~4.Each evaluation is carried out using the sample 1~4, the obtained results are shown in tables 2.
Abbreviation in table 2 is as follows.It should be noted that the "-" in table 2 indicates to be free of the ingredient.
LiTFSI: bis- (trifluoro methylsulfonimide) lithiums, Li (CF3SO2)2N (Morita Chemical Co., Ltd.'s system)
LiTFS: trifluoromethayl sulfonic acid lithium, LiCF3SO3(Morita Chemical Co., Ltd.'s system)
Ionic solid A:N- hexyl pyridine·PF6 ?(there is hexyl pyridine as organic cationIon Organic salt, 45 DEG C of fusing point)
SH-3773M: the dimethyl silica hydride compounds (TorayDow of polyalkylene oxide chain is imported in side chain Corning Co. Ltd. system, the end of polyalkylene oxide chain are hydroxyl, HLB value=8)
Aluminium chelate compound: by praseodynium aluminium (trade name: Aluminum Chelate A, Kawaken Fine Chemical Co. Ltd. system) solution of 9.7 mass % of solid component is diluted to using toluene and acetylacetone,2,4-pentanedione
With comprising acid value in the range of 9mgKOH/g~65mgKOH/g and from the monomer with polyalkylene oxide chain The containing ratio of structural unit relative to entire infrastructure unit quality in the range more than 1 mass % and less than 20 mass % The guarantor of the cross-linking agent of the adhesive composition of the Examples 1 to 23 of (methyl) acrylic acid series polymeric compounds, crosslinking agent and antistatic agent Cuticula, when being used for any adherend, high-rate release property and antistatic property are all excellent.
The especially high-rate release property of the protective film of the cross-linking agent of the adhesive composition with embodiment 6,8,11 and 17 It is more excellent with antistatic property.
In contrast, poly- comprising (methyl) acrylic acid series without the structural unit from the monomer with polyalkylene oxide chain Close object Comparative Examples 1 and 2,7 and 8, and the containing ratio comprising the structural unit from the monomer with polyalkylene oxide chain relative to The quality of entire infrastructure unit is the comparative example 3 of (methyl) acrylic acid series polymeric compounds of 1.0 mass %, is relative to PET's The value of release band voltage is high, and antistatic property is poor.Containing ratio phase comprising the structural unit from the monomer with polyalkylene oxide chain For entire infrastructure unit quality be 20 mass % (methyl) acrylic acid series polymeric compounds comparative example 4 relative to PET's High-rate release property is poor.
In addition, the ratio of (methyl) acrylic acid series polymeric compounds comprising acid value outside the range of 9mgKOH/g~65mgKOH/g It is poor compared with the respective high-rate release property of example 5 and 6.Acid value is the comparative example 6 of 65mgKOH/g or more, and not only high-rate release property, antistatic Property is also poor.
According to the above, the protective film of the cross-linking agent of the adhesive composition with one embodiment of the present invention, no matter by The material of viscous object is how, during needing to protect adherend, the degree that will not fall off from the surface of adherend with protective film Bonding force, while inhibiting bonding force of high speed when removing lower, also, excellent antistatic property.Therefore, have of the invention one The protective film of the cross-linking agent of the adhesive composition of embodiment, no matter the material of adherend, high-rate release property and resist it is quiet It is electrically all excellent.

Claims (7)

  1. It include (methyl) acrylic acid series polymeric compounds, crosslinking agent and antistatic agent 1. a kind of protective film adhesive composition,
    The acid value of (methyl) acrylic acid series polymeric compounds is 9mgKOH/g~65mgKOH/g, also, relative to entire infrastructure list The quality of member, the containing ratio of the structural unit from the monomer with polyalkylene oxide chain are more than 1 mass % and less than 20 mass %.
  2. 2. protective film adhesive composition according to claim 1, wherein (methyl) acrylic acid series polymeric compounds contain The structural unit for thering is the following general formula (1) to indicate,
    In general formula (1), R1Indicate that hydrogen atom or methyl, L are indicated by alkylidene, arlydene, carbonyl and oxygen atom The linking group of the divalent of at least one kind of composition.
  3. 3. protective film adhesive composition according to claim 1 or 2, wherein (methyl) acrylic polymeric Object contains the structural unit from (methyl) alkyl acrylate, described to come from (first relative to the quality of entire infrastructure unit Base) alkyl acrylate structural unit containing ratio be 65 mass of mass %~99 %.
  4. 4. protective film adhesive composition described in any one of claim 1 to 3, wherein it is equal to further include weight (methyl) acrylic oligomers that molecular weight is 3000~20000, relative to 100 matter of (methyl) acrylic acid series polymeric compounds Part is measured, the content of (methyl) acrylic oligomers is 0.05 mass parts~5.00 mass parts.
  5. 5. protective film adhesive composition according to claim 4, wherein (methyl) acrylic oligomers contain There is the structural unit from the monomer with polyalkylene oxide chain, it is described poly- from having relative to the quality of entire infrastructure unit The containing ratio of the structural unit of the monomer of alkylene oxide chain is 5 mass of mass %~30 %.
  6. 6. protective film adhesive composition according to any one of claims 1 to 5, wherein the crosslinking agent is gold Belong to chelate.
  7. 7. a kind of protective film, has adhesive phase and substrate, described adhesive layer is according to any one of claims 1 to 6 The cross-linking agent of protective film adhesive composition.
CN201780001583.1A 2017-09-25 2017-09-25 Adhesive composition for protective film and protective film Active CN109844052B (en)

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JP2008045057A (en) * 2006-08-18 2008-02-28 Toyo Ink Mfg Co Ltd Method for producing acrylic adhesive
JP2010070678A (en) * 2008-09-19 2010-04-02 Dic Corp Adhesive, adhesive film, and surface protective film for optical member
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CN106995670A (en) * 2016-01-26 2017-08-01 日本电石工业株式会社 Diaphragm adhesive composition and diaphragm
CN107129766A (en) * 2016-02-29 2017-09-05 藤森工业株式会社 The preparation method and Antistatic surface diaphragm of Antistatic surface diaphragm

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JP5361244B2 (en) * 2008-05-15 2013-12-04 日本カーバイド工業株式会社 Adhesive composition for optical member surface protective film and optical member surface protective film
JP6673621B2 (en) * 2016-01-19 2020-03-25 日本カーバイド工業株式会社 Pressure-sensitive adhesive composition and optical member surface protection film

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JP2008045057A (en) * 2006-08-18 2008-02-28 Toyo Ink Mfg Co Ltd Method for producing acrylic adhesive
JP2010070678A (en) * 2008-09-19 2010-04-02 Dic Corp Adhesive, adhesive film, and surface protective film for optical member
CN102627918A (en) * 2011-02-04 2012-08-08 日东电工株式会社 Adhesive sheet and surface protective film
CN106995670A (en) * 2016-01-26 2017-08-01 日本电石工业株式会社 Diaphragm adhesive composition and diaphragm
CN107129766A (en) * 2016-02-29 2017-09-05 藤森工业株式会社 The preparation method and Antistatic surface diaphragm of Antistatic surface diaphragm

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