CN109563220A - (methyl) acrylic compounds triblock copolymer and its manufacturing method, adhesive composition and bonding sheet - Google Patents
(methyl) acrylic compounds triblock copolymer and its manufacturing method, adhesive composition and bonding sheet Download PDFInfo
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- CN109563220A CN109563220A CN201780046114.1A CN201780046114A CN109563220A CN 109563220 A CN109563220 A CN 109563220A CN 201780046114 A CN201780046114 A CN 201780046114A CN 109563220 A CN109563220 A CN 109563220A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/387—Block-copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The present invention further improves the adhesive composition containing (methyl) acrylic block copolymer to the bonding physical property of various bonded body.Resulting (methyl) acrylic compounds triblock copolymer (A) is polymerize by using the RAFT of RAFT agent shown in formula (a1).
Description
Technical field
The present invention relates to (methyl) acrylic compounds triblock copolymer and its manufacturing methods, adhesive composition and bonding
Piece.
Background technique
In adhesive field, to the bonding with the bonding physical property such as good retentivity, adhesion strength (Japanese: タ ッ Network)
There are demands for agent composition.Patent Documents 1 to 4 are described containing (methyl) acrylic compounds obtained by living radical polymerization
The adhesive composition of block copolymer.Especially patent document 1 is described containing by using reversible addition fracture chain turn
Move the RAFT polymerization of (RAFT) agent and the adhesive composition of (methyl) acrylic block copolymer of acquisition.But contain
The adhesive composition of this block copolymer requires further improvement the bonding physical property of various bonded body.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2014-208762 bulletin
Patent document 2: Japanese Patent Laid-Open 10-008013 bulletin
Patent document 3: Japanese Patent Laid-Open 2001-348553 bulletin
Patent document 4: Japanese Patent Laid-Open 2016-023237 bulletin
Summary of the invention
The technical problems to be solved by the invention
Technical problem of the invention is further to improve the adhesive group for containing (methyl) acrylic block copolymer
Object is closed to the bonding physical property of various bonded body.
Technical scheme applied to solve the technical problem
The present inventor has made intensive studies to solve above-mentioned technical problem.As a result, it has been found that using having following composition
(methyl) acrylic compounds triblock copolymer be able to solve above-mentioned technical problem, so as to complete the present invention.
The present invention [1] for example, below~[11].
[1] resulting (methyl) acrylic compounds three block is polymerize by using the RAFT of RAFT agent shown in formula (a1)
Copolymer (A).
[changing 1]
In formula (a1), R is free from 1 valence organic group of hydroxyl, carboxyl and amino, and 2 R can be same or different to each other.
[2] (methyl) the acrylic compounds triblock copolymer (A) as described in [1], wherein the R in formula (a1) be alkyl,
Acyl group, acyloxy or acyloxyallcyl.
[3] (methyl) the acrylic compounds triblock copolymer (A) as described in [1] or [2], wherein measured by GPC method
Weight average molecular weight (Mw) is 30,000~600,000, and molecular weight distribution (Mw/Mn) is 1.5~5.0.
[4] (methyl) the acrylic compounds triblock copolymer (A) as described in any one of [1]~[3], with block A-
B block-block A three block structure, B block have the divalent structure indicated with-S-C (=S)-S-, 100 matter of copolymer (A)
It measures in %, total content of block A is 5~40 mass %, and the content of B block is 95~60 mass %.
[5] (methyl) the acrylic compounds triblock copolymer (A) as described in [4], wherein 100 matter of entire infrastructure unit
It measures in %, the content from the structural unit of the monomer containing reactive functional groups is 0.5~15 mass %, from containing anti-
In the 100 mass % of entire infrastructure unit of the monomer of answering property functional group, 95 mass % or more are present in block A.
[6] adhesive composition contains (methyl) acrylic compounds triblock copolymer described in any one of [1]~[5]
Object (A).
[7] adhesive composition as described in [6] also contains curing agent (B).
[8] bonding sheet has the adhesive phase formed by adhesive composition described in [6] or [7].
[9] manufacturing method of (methyl) acrylic compounds triblock copolymer (A) comprising using shown in the formula (a1)
RAFT agent so that the process 1 of the monomer polymerization containing polymeric double bond, into the resulting polymer of process 1 further addition with
The process 2 monomer composition of process 1 the different monomers containing polymeric double bond and polymerize, it is described used in process 1
One or both of the monomer added in monomer and process 2 contains (methyl) acrylate.
[10] manufacturing method of (methyl) the acrylic compounds triblock copolymer (A) as described in [9], wherein obtained by process 1
The weight average molecular weight (Mw) of the polymer obtained measured by GPC method is 3,000~40,000.
[11] manufacturing method of (methyl) the acrylic compounds triblock copolymer (A) as described in [9] or [10], wherein can
In the 100 mass % of monomer containing reactive functional groups used in process 1 and process 2, the list of 95 mass % or more
Body uses in process 1.
Invention effect
By means of the invention it is possible to provide the bonding physical property to various bonded body excellent adhesive composite, in addition can
It is enough that (methyl) the acrylic compounds triblock copolymer containing ingredient for being suitable as the composition is provided.
Specific embodiment
Below to (methyl) acrylic compounds triblock copolymer of the invention and its manufacturing method, adhesive composition and
Bonding sheet and preferable embodiment are described in detail.
In this specification, the meaning of " polymer " includes homopolymer and copolymer, in addition, the meaning of " polymerization " includes homopolymerization
And copolymerization.In addition, acrylic acid and methacrylic acid are referred to as " (methyl) acrylic acid ".
In this specification, the copolymer at least containing the structural unit from (methyl) acrylate is also denoted as " (first
Base) acrylic copolymer ", in the copolymer, it is used to form the copolymer and preferably 70 matter in the starting monomer that uses
Measuring %, the above are (methyl) acrylate.
In this specification, Reversible Addition Fragmentation Chain Transfer is also denoted as " RAFT ".
((methyl) acrylic compounds triblock copolymer (A))
(methyl) acrylic compounds triblock copolymer (A) of the invention is by using RAFT agent shown in formula (a1)
RAFT polymerize to obtain, more particularly by the RAFT for the monomer containing polymeric double bond for including at least (methyl) acrylate
Polymerization obtains.
[changing 2]
In formula (a1), R is free from 1 valence organic group of hydroxyl, carboxyl and amino.2 R can be same or different to each other, but
From the point of view of synthesis, preferably identical group.
R does not have functional group's (hydroxyl, carboxyl and amino) listed above, so that resulting copolymer derives from RAFT
The R does not have functional group listed above yet at the molecular end of agent.
As 1 valence organic group, the alkyl such as alkyl, aryl, aralkyl, R can be enumerated1Acyl shown in-C (=O)-
Base, R1Acyloxy shown in-C (=O)-O-, R1- C (=O)-O-R2Shown in acyloxyallcyl.R1It is alkyl, R2It is alkylene
Base.Wherein, from RAFT agent there is the tendency that is in a liquid state at normal temperature and the good angle of operability, to highly polar or low polar
From the point of view of various bonded body have excellent bonding physical property, preferably acyl group, acyloxy and acyloxyallcyl.
The concrete example of each group is as described below in the 1 valence organic group.The carbon number of alkyl is usually 1~12, and preferably 1
~6, such as methyl, ethyl, propyl, butyl, hexyl can be enumerated.The carbon number of aryl is usually 6~18, and preferably 6~12, example
Phenyl, naphthalene can such as be enumerated.The carbon number of aralkyl is usually 7~18, and preferably 7~12, such as benzyl, phenethyl can be enumerated.
The carbon number of acyl group and acyloxy is usually 2~8, preferably 2~6, such as can enumerate acetyl group, acetoxyl group.Acyloxyallcyl
Carbon number be usually 3~8, preferably 3~6, such as acetoxy-methyl can be enumerated.
As RAFT agent shown in formula (a1), such as compound shown below can be enumerated.
[changing 3]
RAFT agent 1
RAFT agent 2
The RAFT agent has a trithiocarbonic acid ester structure in the molecule, not hydroxyl, carboxyl and amino in the R.Institute
Stating RAFT agent can for example be synthesized by the method for Japanese Patent Laid-Open 2007-230947 bulletin record.
Copolymer (A) preferably has block A- B block-block A three block structure.Herein, B block has with-S-C
(=S)-S- indicate divalent structure.If it is this form, then being capable of forming such as block A is dispersion portion (Japanese: island), embedding
Section B is the island structure or tetrahexahedron (Japanese: ジ ャ イ ロ イ De) structure or cylinder knot of matrix part (Japanese: sea)
Structure can assign adhesive suitable cohesiveness, be preferred from the aspects of.
In 100 mass % of copolymer (A), total content of block A is preferably 5~40 mass %, and more preferably 10~30
Quality %, the content of B block are preferably 95~60 mass %, more preferably 90~70 mass %.
In the 100 mass % of entire infrastructure unit of copolymer (A), from the structure of the monomer containing reactive functional groups
The content of unit is preferably 0.5~15 mass %, more preferably 0.8~12 mass %, further preferably 1~10 mass %.
Structural unit amount for example can be by the polymer solution after each monomer usage amount and polymerization based on gas chromatographic analysis
The residual quantity of each monomer calculates.If it is this form, then adhesive is capable of forming suitable cross-linked form, various bonding physical property
It is excellent, therefore preferably.In addition, the entire infrastructure unit of copolymer (A) is derived from the entire infrastructure unit of starting monomer.
In copolymer (A), in the 100 mass % of entire infrastructure unit of the monomer containing reactive functional groups
95 mass % or more be preferably in block A, more preferable 98 mass % or more is present in block A.If it is this side
Formula, then reactive functional groups concentration is present in block A, so that solidification becomes faster, when can shorten the curing of adhesive composition
Between.
Copolymer (A) is for example indicated with following formula.
[changing 4]
In above formula, R is identical as the meaning of same symbol in formula (a1), and Ap is separately derived from containing polymerism
The divalent group (polymer chain of the monomer containing polymeric double bond) of the polymer of the monomer of double bond, Bp separately come
Derived from the divalent group (polymer chain of the monomer containing polymeric double bond) of the polymer of the monomer containing polymeric double bond.
In above formula, Ap is equivalent to above-mentioned block A ,-Bp-S-C (=S)-S-Bp- and is equivalent to above-mentioned B block.Block A
There is the structural unit from (methyl) acrylate at least one of B block, it is additionally preferred to which both there is source
In the structural unit of (methyl) acrylate.
By using copolymer (A) of the invention, can obtain to highly polar material and the low polarity material of polyolefins etc.
Various bonded body have the adhesive composition of excellent bonds physical property (such as retentivity, adhesion strength).
" monomer containing polymeric double bond "
The starting monomer of copolymer (A) is the monomer containing polymeric double bond at least containing (methyl) acrylate.As
Monomer containing polymeric double bond can enumerate (methyl) acrylate for example without following reactive functional groups, at least have 1
The monomer (being also denoted as " monomer containing reactive functional groups " below) of the following reactive functional groups of kind, being total in addition to these monomers
Poly- property monomer.As the reactive functional groups, acidic group, hydroxyl, amino, amide groups, cyano, nitrogen class heterocycle can be enumerated.
As (methyl) acrylate for not having above-mentioned reactive functional groups, such as (methyl) alkyl acrylate can be enumerated
Ester, (methyl) alkyl acrylate oxygroup alkyl ester, the more alkylene glycols esters of single (methyl) alkyl acrylate oxygroup, containing ester ring type group or
(methyl) acrylate of aromatic ring.
The carbon number of alkyl in (methyl) alkyl acrylate is preferably 1~20.It, can example as (methyl) alkyl acrylate
Citing such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl
Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate,
(methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (first
Base) Isooctyl acrylate monomer, (methyl) nonyl acrylate, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) third
Olefin(e) acid isodecyl ester, (methyl) lauryl ester, (methyl) octadecyl ester, (methyl) acrylic acid isooctadecane ester.
As (methyl) alkyl acrylate oxygroup alkyl ester, such as (methyl) methoxyethyl methyl esters, (methyl) third can be enumerated
Olefin(e) acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) propylene
Sour 3- ethyoxyl propyl ester, (methyl) acrylic acid 4- methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyl.
As the more alkylene glycols esters of list (methyl) alkyl acrylate oxygroup, for example single (methyl) methoxyethyl two can be enumerated
Glycol ester, list (methyl) methoxyethyl dipropylene glycol ester, single (methyl) ethioxy triglycol ester, single (first
Base) ethioxy binaryglycol ester, single (methyl) methoxyethyl triglycol ester.
As (methyl) acrylate containing ester ring type group or aromatic rings, such as (methyl) acrylic acid ring can be enumerated
Own ester, (methyl) isobornyl acrylate, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl)
Benzyl acrylate, (methyl) phenyl acrylate.
Above-mentioned (methyl) acrylate can be used independent a kind, or use two or more.
The usage amount of (methyl) acrylate without above-mentioned reactive functional groups is in addition to containing reactive functional groups
In all 100 mass % of monomer containing polymeric double bond other than monomer, usually more than 70 mass %, preferably in 80 mass %
More than, more preferably more than 90 mass %.
As the monomer containing reactive functional groups, can enumerate for example containing acid-based monomers, hydroxyl monomer, emulsion stability,
Amide-containing monomer, cyano-containing monomer, nitrogenous class heterocyclic monomer.
As containing the acidic group in acid-based monomers, such as carboxyl, anhydride group, phosphate, sulfate can be enumerated.As containing acidic group
Monomer can enumerate such as (methyl) P-carboxy ethyl acrylates, (methyl) acrylic acid 5- carboxyl pentyl ester, succinic acid list (first
Base) acrylyl oxy-ethyl ester, singly carboxylic (methyl) acrylate such as (methyl) acrylic acid ω-carboxy-polycaprolactone；(first
Base) carboxyl group-containing monomers such as unsaturated carboxylic acids such as acrylic acid, itaconic acid, butenoic acid, fumaric acid, maleic acid；Maleic anhydride etc. is containing acid
The monomer of anhydride group；Side chain has the monomer of the phosphorous acidic groups such as (methyl) acrylic monomer of phosphate；Side chain has sulfonic group
(methyl) acrylic monomer etc. contain sulfonic monomer.
As the monomer containing hydroxyl, such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl can be enumerated
Base propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester
(methyl) acrylate of equal hydroxyls.
As emulsion stability, such as (methyl) acrylate, (methyl) acrylic acid diethyl can be enumerated
Amino-containing (methyl) acrylate such as base amino ethyl ester.
As amide-containing monomer, such as (methyl) acrylamide, N- methyl (methyl) acrylamide, N- ethyl can be enumerated
(methyl) acrylic amides such as (methyl) acrylamide, N- propyl (methyl) acrylamide, N- hexyl (methyl) acrylamide.
As cyano-containing monomer, such as cyano (methyl) acrylate, (methyl) acrylonitrile can be enumerated.List as nitrogenous class heterocycle
Body can enumerate such as vinyl pyrrolidone, (methyl) acryloyl morpholine, caprolactam.
In monomer containing reactive functional groups, from from the point of view of the crosslinking reactivity of aftermentioned crosslinking agent (B1), preferably
It is at least one kind of selected from carboxyl group-containing monomer and hydroxyl monomer.
Monomer containing reactive functional groups can be used alone a kind, it is possible to use two or more.
The usage amount of monomer containing reactive functional groups is in the 100 mass % of monomer all containing polymeric double bond, usually
For 0.5~15 mass %, preferably 0.8~12 mass %, more preferably 1~10 mass %.Using selected from carboxyl group-containing monomer and
Hydroxyl monomer it is at least one kind of in the case where, total amount is preferably in the range.
As co-polymerized monomer, such as styrene monomer, vinyl monomer can be enumerated.It, can as styrene monomer
Enumerate such as styrene, α-methylstyrene；The ring-alkylated styrenes such as methyl styrene, dimethyl styrene, octyl styrene；Fluorine
The halogenated styrenes such as styrene, chlorostyrene, bromstyrol；Nitrostyrolene, acetylbenzene ethylene, methoxy styrene.Make
For vinyl monomer, such as vinyl acetate can be enumerated.
Co-polymerized monomer can be used alone a kind, it is possible to use two or more.
" RAFT agent "
In RAFT polymerization, the RAFT agent shown in formula (a1) in the presence of, makes the monomer polymerization containing polymeric double bond.Formula
(a1) usage amount of RAFT agent shown in relative to 100 mass parts of total amount of the monomer containing polymeric double bond be usually 0.05~
20 mass parts, preferably 0.05~10 mass parts.If it is this mode, then reaction is easy to control, in addition resulting copolymer
Weight average molecular weight be readily adjusted to aftermentioned range.
" polymerization initiator "
RAFT polymerization preferably carries out in the presence of polymerization initiator.As polymerization initiator, can enumerate for example conventional
Organic polymerization initiator, can specifically enumerate the peroxide such as benzoyl peroxide, lauroyl peroxide, and 2,2 '-azos two are different
The azo-compounds such as butyronitrile.Wherein, preferably azo-compound.
As azo-compound, such as 2 can be enumerated, 2 '-azodiisobutyronitriles, 2,2 '-azo, two (4- methoxyl group -2,4-
Methyl pentane nitrile), 2,2 '-azos two (2- cyclopropyl propionitrile), 2,2 '-azos two (2,4- methyl pentane nitrile), 2,2 '-azos two
(2- methylbutyronitrile), 1,1 '-azos two (hexamethylene -1- nitrile), 2- (carbamoyl azo) isobutyronitrile, 2- phenylazo -4-
Methoxyl group -2,4- methyl pentane nitrile, two acidified 2,2 '-azos two (2- amidine propane), 2,2 '-azo, two (N, the N methylene of '-two
Base NSC 18620), 2,2 '-azo two (isobutyramide) dihydrates, 4,4 '-azos two (4- cyanopentanoic acid), 2,2 '-azos two
(2- cyano propyl alcohol), dimethyl -2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo, two [2- methyl-N- (2- hydroxyl second
Base)-propionamide].
Polymerization initiator can be used alone a kind, it is possible to use two or more.
The usage amount of polymerization initiator is usually 0.001 relative to 100 mass parts of total amount of the monomer containing polymeric double bond
~2 mass parts, preferably 0.002~1 mass parts.If it is this mode, then the weight average molecular weight of resulting copolymer is easy
It adjusts to aftermentioned range.
" polymer solvent "
RAFT polymerization can be the bulk polymerization without using polymer solvent, can also be as needed in RAFT polymerization using poly-
Bonding solvent.
As polymer solvent, the aromatic hydrocarbon such as benzene,toluene,xylene can be enumerated；Pentane, n-hexane, normal heptane,
The aliphatic hydrocarbons such as normal octane；The ester ring type hydrocarbons such as pentamethylene, hexamethylene, cycloheptane, cyclooctane；Chloroform, carbon tetrachloride, 1,2- dichloro
The halogenated hydrocarbons such as ethane, chlorobenzene；Diethyl ether, diisopropyl ether, 1,2- dimethoxy-ethane, butyl oxide, tetrahydrofuran, dioxanes, benzene
The ethers such as methyl ether, phenetole, diphenyl ether；The esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate；Acetone, methyl ethyl ketone, two
The ketone such as ethyl ketone, methylisobutylketone, cyclohexanone；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone etc.
Amide；The nitriles such as acetonitrile, benzonitrile；The sulfoxides such as dimethyl sulfoxide, sulfolane.
Polymer solvent can be used alone a kind, it is possible to use two or more.
" polymerizing condition "
The manufacturing method of copolymer (A) of the invention is for example including using RAFT agent shown in formula (a1), make containing polymerism
The process 1 (the first RAFT polymerization) of the monomer polymerization of double bond and into the polymer obtained by process 1 further addition and work
The different monomers containing polymeric double bond of the monomer composition of sequence 1 and the process 2 being polymerize (the 2nd RAFT polymerization).In process 1
One or both of the monomer added in the monomer and process 2 used contains (methyl) acrylate, preferably both sides
Contain (methyl) acrylate.
In addition, the monomers containing polymeric double bond different from the monomer composition of process 1 refer to, relative to being used in process 1
Monomer composition, include the case where monomer type and (used in each process, add various of monomer) ratio including process 2 in
Monomer except the identical situation of the monomer composition of addition.For example, the monomer added in monomer used in process 1 and process 2
It can be free of identical monomer.In addition, even if in the identical situation of monomer added in monomer used in process 1 and process 2,
As long as respectively using, be added to used in various of monomer and process 1 single intracorporal ratio (example: methyl acrylate 90wt%, third
Olefin(e) acid butyl ester 10wt%) with the intracorporal ratio of the list (example: methyl acrylate 10wt%, butyl acrylate added in process 2
It is 90wt%) different.
RAFT polymerize when, in the RAFT agent shown in formula (a1) sulphur atom and the methylene adjacent with the sulphur atom it
Between insertion reacted as the mode of the monomer containing polymeric double bond of starting monomer, polymerize.
[changing 5]
The RAFT compound indicated by formula (a1)
The reaction temperature of RAFT polymerization is usually 60~120 DEG C, and preferably 70~110 DEG C, usually in inertia such as nitrogen
It is carried out under gas atmosphere.The reaction can carry out under the conditions of any in normal pressure, pressurization and decompression, usually carry out under normal pressure.
In addition, the reaction time is usually 1~20 hour, preferably 2~14 hours.These conditions can be respectively applied to process 1 and process
2.Polymerizing condition can refer to such as Japanese Patent Laid-Open 2007-230947 bulletin and Japanese Patent Laid-Open 2011-52057
Bulletin.
The weight average molecular weight (Mw) of the resulting polymer of process 1 measured by GPC method is preferably 3,000~40,000,
More preferably 5,000~38,000, further preferably 8,000~36,000.
In addition, can be in the 100 mass % of monomer containing reactive functional groups used in process 1 and process 2, preferably 95 matter
Measure % or more, the monomer containing reactive functional groups of particularly preferred 98 mass % or more is used for process 1.If it is this side
Formula, then reactive functional groups concentration is present in block A, so that solidification becomes faster, when can shorten the curing of adhesive composition
Between.
The ratio of the amount of monomer used in process 1 and process 2 is not particularly limited, such as can be according to as target product
The ratio of the amount of block A and B block in copolymer (A) is suitably set.For example, relative to resulting 100 matter of polymer of process 1
Part is measured, the amount of the monomer containing polymeric double bond added in process 2 is preferably 150~1900 mass parts, more preferably 233~
900 mass parts.
[physical property of copolymer (A)]
The weight average molecular weight (Mw) of copolymer (A) measured by gel permeation chromatography (GPC method) is preferably 30,000
~600,000, more preferably 50,000~550,000, further preferably 80,000~500,000.If it is this shape
State then can sufficiently assign adhesive composition cohesiveness, the durability under the conditions of high temperature drying and under the conditions of high temperature and humidity
It is preferred from the point of view of raising.
The molecular weight distribution (Mw/Mn) of copolymer (A) is preferably 1.5~5.0, and more preferably 1.5~4.8, it is further excellent
It is selected as 1.7~4.5.If it is this mode, then the excellent heat resistance of resulting crosslinked and/or solidified body, and can press down
The pollution of bonded body when bonding sheet processed is removed.
Molecular weight and molecualr weight distribution can be measured according to the condition recorded in embodiment.
The glass transition temperature (Tg) of copolymer (A) is preferably shorter than 0 DEG C, more preferably -70~-20 DEG C, further preferably -
60~-30 DEG C.If Tg is preferred from the point of view of the adaptation from adhesive phase to clung body in the range.
If being excellent from the point of view of from the cohesiveness of adhesive phase, excellent, durability is improved in addition, Tg is more than the lower limit value
Choosing.The Tg of copolymer (A) can for example be calculated by Tg the and Fox formula of the homopolymer of each monomer.The Tg of the homopolymer of each monomer
It is able to use institute in such as " polymer handbook " (Polymer Handbook) fourth edition (Wiley-Interscience 2003)
The numerical value of record.
In one embodiment, preferably -30~150 DEG C of the Tg of block A, more preferably -20~120 DEG C, B block
Tg is preferably -80~-40 DEG C, more preferably -75~-50 DEG C.The Tg of each block for example can be by the Tg of the homopolymer of each monomer
It is calculated with Fox formula.
In addition, not being recorded in the monomer in above-mentioned document for Tg, such as can be measured by the following conditions by following item
The Tg of the homopolymer of part synthesis.It is added into the reaction unit for having blender, reflux cooler, thermometer and nitrogen ingress pipe
100 mass parts monomers and 100 mass parts ethyl acetate solvents, are warming up to 80 DEG C while importing nitrogen.Then, it is added 0.1
The 2 of mass parts, 2 '-azodiisobutyronitriles carry out 6 hours polymerization reactions in nitrogen atmosphere at 80 DEG C.It will be resulting equal
The enclosed simple closed flat chassis of polymers.Using differential scanning calorimetry (DSC) (DSC), with 10 DEG C/min of speed under stream of nitrogen gas
Heating draws the chart of " heat absorption calorific value " and " temperature ", the characteristic flexural observed at this time is changed conduct to measure thermal change
Glass transition.In addition, Tg uses the value obtained by mid-point method by DSC curve.
(adhesive composition)
Adhesive composition of the invention contains above-mentioned (methyl) acrylic compounds triblock copolymer (A).It is preferred that the present invention
Adhesive composition can also contain depending on the application curing agent (B).
[(methyl) acrylic compounds triblock copolymer (A)]
Adhesive composition solid component of the content of (methyl) acrylic compounds triblock copolymer (A) in 100 mass %
In usually more than 60 mass %, preferably more than 65 mass %, more preferably more than 70 mass %.In addition, copolymer (A)
The upper limit value of the content can also be that 100 mass % depend on other compositions in the case where containing other compositions in solid component
Content.If it is this mode, it is from the point of view of it can arbitrarily adjust the various bonding physical property such as retentivity, adhesion strength then
Preferably.Solid component typically refers to the ingredient other than solvent.
[curing agent (B)]
It is preferred that adhesive composition of the invention also contains curing agent (B).Copolymer (A) is crosslinked by curing agent (B)
And/or solidify composition, it is capable of forming crosslinked and/or solidified body whereby, the adhesive phase of excellent heat resistance can be obtained.
Adhesive composition of the invention can be any one of heat cure class and active energy ray-curable class.
The type of curing agent (B) is consolidated according to the reactive functional groups and adhesive composition that can import copolymer (A)
Change classification suitably to select.For example, being able to use isocyanide in the case that acrylic copolymer (A) has reactive functional groups
Ester compound, epoxide, metallo-chelate etc. can be with the crosslinking agents (B1) of functional group's cross-linking reaction.In addition,
As curing agent (B), it is able to use such as multifunctional (methyl) acrylate (B2).
As isocyanate compound, usually using isocyanates chemical combination of the isocyanate group quantity 2 or more in 1 molecule
Object, the isocyanate group quantity is preferably 2~8, and more preferably 3~6.If isocyanate group quantity in the range,
Then examined from copolymer (A) and the angle of the cross-linking reaction efficiency of isocyanate compound and the flexibility of holding adhesive phase
Worry is preferred.
The diisocyanate cpd for being 2 as isocyanate group quantity in 1 molecule can enumerate for example aliphatic two isocyanides
Acid esters, alicyclic diisocyanate, aromatic diisocyanates.As aliphatic diisocyanate, ethylene isocyanide can be enumerated
Acid esters, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2- methyl-1,5- pentane
Diisocyanate, 3- methyl-1, the carbon such as 5- pentane diisocyanate, 2,2,4- trimethyl -1,6- hexamethylene diisocyanate
The aliphatic diisocyanate that number is 4~30.As alicyclic diisocyanate, isophorone diisocyanate, ring can be enumerated
Amyl diisocyanate, cyclohexyl diisocyanate hydrogenate sub- xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogen
Change alicyclic two isocyanide that the carbon numbers such as '-diphenylmethane diisocyanate, hydrogenation tetramethyl Asia xylene diisocyanate are 7~30
Acid esters.As aromatic diisocyanates, such as phenylene vulcabond, toluene di-isocyanate(TDI), sub- dimethylbenzene two can be enumerated
Isocyanates, naphthalene diisocyanate, diphenyl ether diisocyanate, '-diphenylmethane diisocyanate, diphenylpropane diisocyanate
The aromatic diisocyanates that equal carbon numbers are 8~30.
As isocyanate compound of the isocyanates radix 3 or more in 1 molecule, such as aromatics polyisocyanate can be enumerated
Ester, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate.It is different that tri- toluene isocyanate of 2,4,6-, 1,3,5- tri- can specifically be enumerated
Phenyl-cyanate, 4,4 ', 4 "-triphenylmethane triisocyanates.
In addition, above-mentioned isocyanide of such as isocyanate group quantity 2 or 3 or more can be enumerated as isocyanate compound
The polymer (such as dimer or tripolymer, biuret body, isocyanuric acid ester body) of ester compound, derivative are (such as polynary
The addition reaction product of diisocyanate cpd more than alcohol and 2 molecules), polymer.As polynary in the derivative
Alcohol, low molecular weight polyols can enumerate the alcohol of the ternary such as trimethylolpropane, glycerine, pentaerythrite or more；Macromolecule
Weight polyalcohol can enumerate such as polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, poly- isoamyl two
Alkene polyalcohol.
This isocyanate compound can enumerate the tripolymer of such as '-diphenylmethane diisocyanate, polymethylene polyphenyl base
The biuret body or isocyanuric acid ester body of polyisocyanate, hexamethylene diisocyanate or toluene di-isocyanate(TDI), three hydroxyl first
Reaction product (such as toluene di-isocyanate(TDI) or the Asia of base propane and toluene di-isocyanate(TDI) or sub- xylene diisocyanate
Three molecule addition products of xylene diisocyanate), the reaction product (example of trimethylolpropane and hexamethylene diisocyanate
Such as three molecule addition products of hexamethylene diisocyanate), polyethers polyisocyanate, polyester polyisocyanate.
In isocyanate compound, from the point of view of difficult xanthochromia, preferred eylylene diisocyanate class and six
The crosslinking agent of methylene diisocyanate class, from the point of view of stress retentivity, the preferably crosslinking of toluene di-isocyanate(TDI) class
Agent.As eylylene diisocyanate class crosslinking agent, such as eylylene diisocyanate and its polymer can be enumerated
Or derivative, polymer；As hexamethylene diisocyanate class crosslinking agent, can enumerate such as hexamethylene diisocyanate and
Its polymer or derivative, polymer；As toluene di-isocyanate(TDI) class crosslinking agent, can enumerate such as toluene di-isocyanate(TDI) and
Its polymer or derivative, polymer.
As epoxide, the compound in molecule with 2 or more epoxy groups can be enumerated, such as ethylene glycol can be enumerated
Diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6- oneself two
Alcohol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diamino glycidyl amine, N,
N, N', N'- four glycidyl group m-xylene diamine, 1,3- bis- (N, N'- diamino glycidyl-amino methyl).
As metallo-chelate, can enumerate such as alkoxide, acetylacetone,2,4-pentanedione, ethyl acetoacetate to aluminium, iron, copper, zinc,
Compound made of the polyvalent metal coordinations such as tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium.Specifically, aluminium isopropoxide, secondary can be enumerated
Butyric acid aluminium, oacetic acid aluminium diisopropyl ester, aluminium tris(ethylacetoacetate), praseodynium aluminium.
As polyfunctional group (methyl) acrylate (B2), such as two, three or multi alkylidene diol-two (methyl) can be enumerated
Acrylate, two (methyl) acrylic acid alkane diol esters, bisphenols two (methyl) acrylate, more than 3 functions more (methyl)
Acrylic acid multielement alcohol ester, polyurethanes two (methyl) acrylate, more (methyl) acrylate of polyurethanes.
Curing agent (B) can be used alone a kind, it is possible to use two or more.
In adhesive composition of the invention, relative to 100 mass parts of copolymer (A), the content of curing agent (B) is usual
For 0.01~25 mass parts, preferably 0.05~20 mass parts, the more preferably range of 0.1~15 mass parts.
In one embodiment, copolymer of the content of crosslinking agent (B1) relative to 100 mass parts in the composition
It (A) is preferably 0.01~5.0 mass parts, more preferably 0.05~4.0 mass parts, further preferably 0.1~3.0 mass parts
Range.Or in another embodiment, in the composition multifunctional (methyl) acrylate (B2) relative to 100 mass
The content of the copolymer (A) of part is preferably 0.01~20 mass parts, more preferably 0.05~15 mass parts, further preferably
The range of 0.1~10 mass parts.If it is this range, then it can be realized the degree of cross linking appropriate, curing degree, can be realized excellent
Bond properties, therefore preferably.
[Photoepolymerizationinitiater initiater (C)]
Adhesive composition of the invention can also contain Photoepolymerizationinitiater initiater (C).For example, at least containing multifunctional (methyl)
Acrylate (B2) contains the composition of Photoepolymerizationinitiater initiater (C) as curing agent (B), also preferably as active energy beam
Solidify class adhesive composition.
As Photoepolymerizationinitiater initiater (C), such as benzoin ethers Photoepolymerizationinitiater initiater, acetophenones photopolymerization can be enumerated and drawn
Send out agent, benzophenone Photoepolymerizationinitiater initiater, ketal class Photoepolymerizationinitiater initiater, thioxanthene ketone class Photoepolymerizationinitiater initiater, acyl group oxidation
Phosphine Photoepolymerizationinitiater initiater can enumerate Japanese Patent Laid-Open 2009-013361 bulletin as the concrete example of these initiators
The compound enumerated in paragraph [0023]~[0027].
Photoepolymerizationinitiater initiater (C) can be used alone a kind, it is possible to use two or more.
In a kind of embodiment of adhesive composition of the invention, relative to multifunctional (methyl) acrylate (B2)
100 mass parts, the content of Photoepolymerizationinitiater initiater (C) are usually 0.1~200 mass parts, and preferably 10~150 mass parts are more excellent
It is selected as the range of 20~100 mass parts.
[additive (D)]
Adhesive composition of the invention in addition to the above ingredients, within the scope of the effect of the invention, may be used also
Containing (methyl) acrylic polymer being selected from addition to copolymer (A), tackifying resin, silane coupling agent, antistatic agent, resist
Oxidant, light stabilizer, preventing metal corrosion agent, plasticizer, crosslinking accelerator, surfactant and heavy industry remover (Japanese:
リ ワ ー Network drug) in one kind or two or more additive.
[organic solvent (E)]
Adhesive composition of the invention preferably comprises organic solvent (E) to adjust its coating.Of the invention is viscous
In mixture composite, the content of organic solvent (E) is usually 30~90 mass %, preferably 40~90 mass %.As organic
Solvent (E), can enumerate the solvent enumerated as above-mentioned polymer solvent.
Organic solvent (E) can be used alone a kind, it is possible to use two or more.
[preparation of adhesive composition]
Adhesive composition of the invention can for example be prepared by mixing above-mentioned each ingredient by a conventionally known method.
For example, the solution containing the copolymer (A) synthesized by copolymer (A) and other compositions can be mixed viscous to prepare
Mixture composite.
(bonding sheet)
Bonding sheet of the invention has the adhesive phase formed by adhesive composition of the invention.
As bonding sheet, the double-sided adhesive sheet for example only with above-mentioned adhesive phase can be enumerated, there is substrate and be formed in
The adhesive phase of adhesive phase and at least one party on substrate two sides is the bonding that adhesive composition through the invention is formed
The double-sided adhesive sheet of oxidant layer, the single side bonding sheet with substrate and the above-mentioned adhesive phase being formed in the one side of substrate and
These bonding sheets are pasted with the bonding sheet of the cover film by lift-off processing on the face of adhesive phase not contacted with substrate.
The thickness of adhesive phase is usually 5~200 μm from the point of view of maintaining bond properties, preferably 10~100 μ
m.In addition, the gel fraction of adhesive phase is preferably 10~98 matter from the point of view of cohesiveness, bonding force and releasable
Measure %, more preferably 20~95 mass %, further preferably 30~90 mass %.
For example, by carrying out being crosslinked in adhesive composition of the invention and/or curing reaction, in a certain embodiment
Middle copolymer (A) is crosslinked by crosslinking agent (B1), obtains above-mentioned adhesive phase whereby.
The formation condition of adhesive phase is for example as described below.Adhesive composition of the invention is coated on substrate, supporter
Or on cover film.In the case that the composition contains solvent, in usually 50~150 DEG C, preferably 60~100 DEG C of temperature
The lower drying for carrying out usually 1~10 minute, preferably 2~7 minutes is to remove solvent.Film is formed in the above manner.
As the coating method of adhesive composition, well known method can be used, such as pass through spin-coating method, cutter painting method, roller
Coating, stick coating method, scraper coating, die coating method, gravure coating method, the side for being coated and drying in a manner of reaching specific thickness
Method.
In the case where heat cure class adhesive composition, it can be existed with the time of usual 3 days or more, preferably 7~10 days
It is carried out in the environment of usual 5~60 DEG C, preferably 15~40 DEG C of temperature and usual 30~70%RH, preferably 40~70%RH
Maintenance.If be crosslinked by the cooking conditions, crosslinked (network polymers) can be efficiently formed.
In the case where active energy ray-curable class adhesive composition, by irradiating active-energy on above-mentioned film
Ray can obtain adhesive.As the active energy beam, such as ultraviolet light, luminous ray and electron ray can be enumerated, it is excellent
Select ultraviolet light.As the irradiation condition of active energy beam, accumulated light is usually 300~3000mJ/cm2。
In addition, above-mentioned curing and active energy beam irradiation are preferably above-mentioned by substrate, supporter or cover film clamping
It is carried out in the state of film, to completely cut off contact of the above-mentioned film with air.
As substrate, supporter and cover film, such as plastic foil, foaming body substrate, non-woven fabrics, paper, flat filament cloth can be enumerated.
As plastic foil, the polyester film such as polyethylene terephthalate can be enumerated；Polyethylene, polypropylene, ethane-acetic acid ethyenyl
The polyolefin films such as ester copolymer.As foaming body substrate, can enumerate for example using polyethylene, polypropylene, ethylene-propylene copolymer
The resulting foaming body substrate of the olefine kind resins such as object, vinyl-vinyl acetate copolymer uses the resulting foaming body of polystyrene
Substrate, using the resulting foaming body substrate of polyurethane, use the resulting foaming body substrate of polyvinyl chloride, use (methyl) acrylic acid
The resulting foaming body substrate of class rubber uses the resulting foaming body substrate such as other elastomers.As non-woven fabrics, can enumerate for example
It is fine using the chemistry such as abaca, wood pulp, artificial silk, typel, polyester fiber, vinal, Fypro
Non-woven fabrics obtained by the mixture of more than two kinds of dimension and these fibers.As flat filament cloth, can enumerate for example flat to polyethylene
Cloth obtained by silk, polypropylene flat-filament are weaved, and the cloth obtained by its surface laminated resin film.Substrate, supporter and
The thickness of cover film is not particularly limited, and for example, 5~150 μm.
(purposes)
The bonding force of bonding sheet of the invention and the balance of releasable are excellent.
Bonding sheet of the invention has the bonding on highly polar material and the low polarity material of polyolefins good
It is bonded physical property.As the low polarity material of polyolefins, such as polyethylene, polypropylene can be enumerated.Therefore, bonding sheet energy of the invention
It is enough widely used as industrial bonding sheet, especially can be used for the nonwoven used in the interior dress and electronic equipment internal of automobile
Distributing double-sided adhesive tape and urethane foam are bonded purposes.
Embodiment
More specific description is carried out to the present invention below based on embodiment, but the present invention is not limited to these embodiments.With
In lower record, unless otherwise instructed, then " part " expression " mass parts ".
Each measured value in embodiment acquires in accordance with the following methods.
(measurement of heating residual component)
1g polymer solution is added into the tin plating iron pan (quality: n1) of accurate weighing, accurate weighing adds up to quality (n2)
Afterwards, it is heated 3 hours at 150 DEG C.Later, which is placed in drier at room temperature and stands 1 hour, it is then smart again
It really weighs, the gross mass (n3) after measurement heating.Using obtained mass determinations (n1~n3), it is residual that heating is calculated by following formula
Profit retention point.
Heating residual component (quality %)=
100 × [quality (n2-n1) before quality (n3-n1)/heating after heating]
(weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn))
For (methyl) acrylic copolymer, standard polystyren conversion is acquired under the following conditions using GPC method
Mw and Mw/Mn.
Measurement device: HLC-8120GPC (TOSOH Co., Ltd (Dong ソ ー (strain)) production)
The composition of GPC column: 5 pedestal (all being produced by TOSOH Co., Ltd) below
(1) TSK-GEL HXL-H (guard column)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
Sample solution concentration: 1.0mg/cm is diluted to using tetrahydrofuran3
Mobile phase solvent: tetrahydrofuran
Flow: 1.0cm3/min
Column temperature: 40 DEG C
[embodiment A1]
Methyl acrylate is added into the flask equipped with agitating device, nitrogen ingress pipe, thermometer and the cooling tube that flows back
(MA) 90g, acrylic acid (AA) 10g, ethyl acetate 30g and 1.0g RAFT agent 1 shown in following formula, import into flask on one side
The content of flask is heated to 80 DEG C on one side by nitrogen.
[changing 6]
RAFT agent 1
Then, 2, the 2 '-azodiisobutyronitriles for adding 0.02g into flask under stiring, make the content in flask
Temperature be able to maintain that the heating and cooling carried out under conditions of 80 DEG C 1 hour.
Heating in 10 hours is carried out under conditions of being able to maintain that the temperature of the content in flask at 80 DEG C later
And cooling, finally add 20 parts of ethyl acetate.
The polymer solution containing acrylate copolymer (A') is obtained as described above.The heating of resulting polymer solution is residual
Profit retention is divided into about 65 mass %.The Mw of the acrylate copolymer (A') contained in resulting polymer solution is 25,000.
In addition, prepare the flask that agitating device, nitrogen ingress pipe, thermometer and reflux condensing tube are housed, it is poly- with acrylic acid
The solid component for closing object (A') reaches the polymer solution that the condition addition of 15g contains acrylate copolymer (A'), is then added
The content of flask is heated to by n-butyl acrylate (BA) 85g, ethyl acetate 50g while importing nitrogen into flask
80℃。
Then, 2, the 2 '-azodiisobutyronitriles for adding 0.02g into flask under stiring, make the content in flask
Temperature be able to maintain that the heating and cooling carried out under conditions of 80 DEG C 1 hour.
Heating in 10 hours is carried out under conditions of being able to maintain that the temperature of the content in flask at 80 DEG C later
And cooling, finally add 20 parts of ethyl acetate.
The polymer solution containing acrylate copolymer (A1) is obtained as described above.The heating of resulting polymer solution is residual
Profit retention is divided into about 52 mass %.The Mw of the acrylate copolymer (A1) contained in resulting polymer solution is that 17, Mw/Mn is
2.1。
[embodiment A2]
Other than using acrylic acid (AA) described in acrylic acid 4- hydroxybutyl (4HBA) substitution tables 1, with embodiment A1
The polymer solution containing acrylate copolymer (A2) is got similarly.
[Comparative examples A 1]
N-butyl acrylate is added into the flask equipped with agitating device, nitrogen ingress pipe, thermometer and the cooling tube that flows back
(BA) 85g, methyl acrylate (MA) 13.5g, acrylic acid (AA) 1.5g, ethyl acetate 100g, import nitrogen into flask on one side
The content of flask is heated to 80 DEG C on one side by gas.
Then, 2, the 2 '-azodiisobutyronitriles for adding 0.05g into flask under stiring, make the content in flask
Temperature be able to maintain that the heating and cooling carried out under conditions of 80 DEG C 1 hour.
Heating in 10 hours is carried out under conditions of being able to maintain that the temperature of the content in flask at 80 DEG C later
And cooling, it is finally diluted with ethyl acetate, is prepared for the copolymer solution containing copolymer (RA1).Resulting copolymer
(RA1) Mw is 240,000, Mw/Mn 4.5.
[Comparative examples A 2]
Other than the acrylic acid (AA) for using acrylic acid 4- hydroxybutyl (4HBA) substitution tables 1 to record, with Comparative examples A 1
The polymer solution containing acrylate copolymer (RA2) is got similarly.
< adhesive composition and bonding sheet >
[embodiment B1, B2 and comparative example B1, B2]
The resulting polymer solution such as embodiment is used as uncrosslinked adhesive composition.In addition, by the institutes such as embodiment
The polymer solution obtained and M-5A, E-50C or L-45 as crosslinking agent (are that Soken Chemical & Engineering Co., Ltd. is (comprehensive to grind chemistry
(strain)) system) it is mixed in such a way that the solid component concentration of crosslinking agent reaches the amount of Table 1, it is suitably diluted, is obtained with ethyl acetate
Adhesive composition associated with handing over.
After adhesive composition is defoamed, using blade coating in thick 50 μm of polyethylene terephthalate (PET)
The implementation of film on the face of sided corona treatment it is 5 minutes dry at 90 DEG C so that dry film thickness reaches 50 μm, eliminate solvent.It will
Resulting adhesive film fits in the PET diaphragm that lift-off processing is crossed, and cures 7 days, obtains in the environment of 23 DEG C and 65%RH
Bonding sheet.
< evaluates >
(retentivity test)
Under conditions of 23 DEG C and 50%RH, the PET diaphragm of the obtained bonding sheet in embodiment etc. is removed, in SUS
The adhesive phase that exposing is pasted on plate is crimped round-trip 3 times with the roller of 2kg.Bonding area is 20mm × 20mm.It pastes
After twenty minutes, under 80 DEG C and drying condition, apply the loading of 500g to uncrosslinked system along parallel direction to adhesive level,
Apply the loading of 1kg to cross-linking system, measurement applies the distance (mm) deviateed after loading starts 1 hour from original position.In addition,
When falling of piece has occurred in minute, describes lowering time.In addition, for not carrying out institute under E-50C addition system
Piece, the piece after the curing 2 days, the piece after 3 days stating curing in 7 days and preparing also have carried out retentivity test.
(probe adhesion test (Japanese: プ ロ ー Block タ ッ ク Shi test))
The PET diaphragm for removing the resulting bonding sheets such as embodiment, determines the probe adhesion strength of the adhesive phase of exposing.It visits
Needle diameter is 5mm, is SUS system, and time of contact is 1 second, and probe speed is 1cm/ seconds, loading 20g.
(gel fraction)
Other than the PET diaphragm substitution PET film for using lift-off processing to cross is made, equally obtained from embodiment etc.
Bonding sheet remove PET diaphragm, from resulting adhesive phase acquire about 0.1g adhesive be added sample bottle, add ethyl acetate
30mL and after vibrating 4 hours, with the content of the 200 purposes stainless steel metal mesh filter sample bottle, to metal at 100 DEG C
Online residue is 2 hours dry, determines dry mass.The gel fraction of adhesive is found out using following formula.Add about E-50C
Add system, found out do not carry out curing in described 7 days and prepare piece, the piece after the curing 2 days, piece after 3 days gel point
Number.
Gel fraction (%)=(dry mass/adhesive acquisition quality) × 100 (%)
[table 1]
Table 1
M-5A: aluminium chelate compound class crosslinking agent
E-50C: epoxies crosslinking agent
L-45: isocyanates crosslinking agent
[table 2]
The curing of 2 embodiment B1 of table, comparative example B1 E-50C addition system
After ※ coating at once: the measurement of " after coating, 90 DEG C of dryings in 5 minutes at once "
The cohesion of the bonding sheet of the embodiment B1 and embodiment B2 that are prepared by the copolymer of embodiment A1 and embodiment A2
Power is higher than the bonding sheet of comparative example B1 and comparative example B2 by comparing example A1 and the preparation of the copolymer of Comparative examples A 2, it can thus be appreciated that
Even if uncrosslinked also have sufficient retentivity.Although in addition, the monomer composition phase of embodiment A1 and the copolymer of Comparative examples A 1
Together, but in the case where structure present in the reactive functional groups collection as embodiment A1, it is excellent that curing property can be obtained
Bonding sheet.
Claims (11)
1. (methyl) acrylic compounds triblock copolymer obtained by the RAFT polymerization by using RAFT agent shown in formula (a1)
(A),
[changing 1]
In formula (a1), R is free from 1 valence organic group of hydroxyl, carboxyl and amino, and 2 R can be same or different to each other.
2. (methyl) acrylic compounds triblock copolymer (A) as described in claim 1, which is characterized in that the R in formula (a1) is
Alkyl, acyl group, acyloxy or acyloxyallcyl.
3. (methyl) acrylic compounds triblock copolymer (A) as claimed in claim 1 or 2, which is characterized in that pass through GPC method
The weight average molecular weight (Mw) of measurement is 30,000~600,000, and molecular weight distribution (Mw/Mn) is 1.5~5.0.
4. (methyl) acrylic compounds triblock copolymer (A) according to any one of claims 1 to 3, which is characterized in that tool
There is block A- B block-block A three block structure,
B block has the divalent structure indicated with-S-C (=S)-S-,
In 100 mass % of copolymer (A), total content of block A is 5~40 mass %, and the content of B block is 95~60 matter
Measure %.
5. (methyl) acrylic compounds triblock copolymer (A) as claimed in claim 4, which is characterized in that entire infrastructure unit
In 100 mass %, the content from the structural unit of the monomer containing reactive functional groups is 0.5~15 mass %, is derived from
In the 100 mass % of entire infrastructure unit of monomer containing reactive functional groups, 95 mass % or more are present in block A.
6. adhesive composition, which is characterized in that contain (methyl) acrylic compounds three according to any one of claims 1 to 5
Block copolymer (A).
7. adhesive composition as claimed in claim 6, which is characterized in that also contain curing agent (B).
8. bonding sheet, which is characterized in that the adhesive phase formed with the adhesive composition as described in claim 6 or 7.
The manufacturing method of (9. methyl) acrylic compounds triblock copolymer (A), which is characterized in that including using shown in formula (a1)
RAFT agent so that the process 1 of the monomer polymerization containing polymeric double bond, into the resulting polymer of process 1 further addition and work
The process 2 monomer composition of sequence 1 the different monomers containing polymeric double bond and polymerize, the list used in process 1
One or both of the monomer added in body and process 2 contains (methyl) acrylate,
[changing 2]
In formula (a1), R is free from 1 valence organic group of hydroxyl, carboxyl and amino, and 2 R can be same or different to each other.
10. the manufacturing method of (methyl) acrylic compounds triblock copolymer (A) as claimed in claim 9, which is characterized in that by
The weight average molecular weight (Mw) of the polymer that process 1 obtains measured by GPC method is 3,000~40,000.
11. the manufacturing method of (methyl) the acrylic compounds triblock copolymer (A) as described in claim 9 or 10, feature exist
In, it can be in the 100 mass % of monomer containing reactive functional groups used in process 1 and process 2, the institute of 95 mass % or more
The monomer containing reactive functional groups is stated to use in process 1.
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| JP2016-152661 | 2016-08-03 | ||
| JP2016152661 | 2016-08-03 | ||
| PCT/JP2017/027714 WO2018025808A1 (en) | 2016-08-03 | 2017-07-31 | (meth)acrylic triblock copolymer and manufacturing method of same, adhesive composition and adhesive sheet |
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| CN109563220A true CN109563220A (en) | 2019-04-02 |
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| JP (1) | JP7089471B2 (en) |
| KR (1) | KR102418362B1 (en) |
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| CN115466585A (en) * | 2021-12-25 | 2022-12-13 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
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| JP2007230947A (en) * | 2006-03-02 | 2007-09-13 | Nippon Terupen Kagaku Kk | Dibenzyl trithiocarbonate derivative, method for producing the same and polymer by using the same |
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| JPH108013A (en) | 1996-04-23 | 1998-01-13 | Sekisui Chem Co Ltd | Acrylic adhesive composition |
| JP4768103B2 (en) | 2000-06-06 | 2011-09-07 | 日東電工株式会社 | Adhesive composition, its adhesive sheet and method for producing them |
| JP2011052057A (en) * | 2009-08-31 | 2011-03-17 | Nippon Terupen Kagaku Kk | Method for producing raft polymer, raft polymer, and polymer using the same |
| JP5671500B2 (en) * | 2012-07-02 | 2015-02-18 | 綜研化学株式会社 | Resin composition, pressure-sensitive adhesive, and polymer production method |
| JP6028741B2 (en) | 2013-03-28 | 2016-11-16 | 藤倉化成株式会社 | Adhesive composition |
| CN105247004B (en) * | 2013-05-28 | 2017-09-26 | 综研化学株式会社 | Adhesive composition and bonding sheet |
| JP5820512B1 (en) | 2014-07-18 | 2015-11-24 | 積水化学工業株式会社 | Structure-controlled block copolymer, adhesive and adhesive tape |
| JP7106244B2 (en) * | 2015-10-29 | 2022-07-26 | 三菱ケミカル株式会社 | Adhesive composition, peelable adhesive obtained using the same, peelable adhesive sheet, and method of using the peelable adhesive sheet |
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| US20040006151A1 (en) * | 2000-07-28 | 2004-01-08 | Marc Husemann | Adhesive material based on block copolymers having a structure p(a/c)-p(b)-p(a/c) |
| JP2007230947A (en) * | 2006-03-02 | 2007-09-13 | Nippon Terupen Kagaku Kk | Dibenzyl trithiocarbonate derivative, method for producing the same and polymer by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115466585A (en) * | 2021-12-25 | 2022-12-13 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
| CN115466585B (en) * | 2021-12-25 | 2023-11-10 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
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| Publication number | Publication date |
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| JPWO2018025808A1 (en) | 2019-05-30 |
| KR102418362B1 (en) | 2022-07-07 |
| WO2018025808A1 (en) | 2018-02-08 |
| JP7089471B2 (en) | 2022-06-22 |
| KR20190036527A (en) | 2019-04-04 |
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