CN105829479B - Acrylic adhesive composition and adhesive tape - Google Patents
Acrylic adhesive composition and adhesive tape Download PDFInfo
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- CN105829479B CN105829479B CN201580003157.2A CN201580003157A CN105829479B CN 105829479 B CN105829479 B CN 105829479B CN 201580003157 A CN201580003157 A CN 201580003157A CN 105829479 B CN105829479 B CN 105829479B
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- Prior art keywords
- triblock copolymer
- segment
- adhesive composition
- copolymer
- mass
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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
- 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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
Abstract
The present invention provides the acrylic adhesive composition for being capable of the excellent adhesive tape of being fixed property.The adhesive composition of the present invention, it contains：The ABA type triblock copolymer (a) of segment B comprising the segments A based on methacrylate and based on acrylate, the ABA type triblock copolymer (b) of segment B comprising the segments A based on methacrylate and based on acrylate, with the tackifying resin (c) for being more than 110 DEG C with the softening point of above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b) with compatibility, the adhesive composition has composition monomer of the ethylhexyl of acrylic acid 2 as the segment B of above-mentioned triblock copolymer (b), above-mentioned triblock copolymer (b) is more than 0.1 mass % and below 50 mass % relative to the match ratio of above-mentioned triblock copolymer (a) and the total amount of above-mentioned triblock copolymer (b).
Description
Technical field
The present invention relates to a kind of adhesive composition, more specifically, be related to a kind of acrylic adhesive composition and
The adhesive composition is coated on the adhesive tape that base material forms.
Background technology
The acrylic adhesive formed containing (methyl) acrylic ester monomer have weatherability, the transparency, heat resistance,
Solvent resistance etc. is excellent and can be by changing the advantages of composition of formed monomer is easily to control bonding force, therefore
Energetically studied in recent years (referring for example to Japanese documentation 1~3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-307063 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-102467 publications
Patent document 3：Japanese Unexamined Patent Publication 2006-206624 publications
The content of the invention
Invention technical problems to be solved
Here, as to the representational practical characteristic required by adhesive tape, can generally enumerate bonding force (peel strength),
Sticky (cohesive) and three fundamental characteristics of confining force (cohesiveness), it is different according to the purposes of adhesive tape, except above-mentioned fundamental characteristics
Outside, this characteristic of stationarity is also required sometimes.As such a fixed one, can enumerate for example：(such as declared thing will be attached
Pass the stationery such as picture) be attached at as defined in be such as resistant to caused by attaching face (such as wall) by attaching thing relaxation or
Stress caused by warpage, as caused by gravity the shearing force of vertical direction (attaching thing not peel off from by the face of attaching) characteristic (with
Under, it is recited as " shearing stationarity ".)；Or when attaching thing (such as the stationery such as ground paper) is fixed as into tubular isotactic setting shape
(attaching thing not peel off each other) characteristic (following, record of the caused repulsive force for being such as resistant to want to return to original form
For " repulsion stationarity ".) etc..That is, stationarity said here refers to：And the characteristic of non-adhesive in itself, but be resistant to
The regulation external force such as stress, gravity, repulsive force as described above (can also maintain to attach in the case of regulation external force is applied
Have the state for attaching thing) characteristic.
For the acrylic adhesive composition described in above-mentioned patent document 1~3, although current situation be with
Practical level has as described above to the fundamental characteristics required by adhesive tape, but in the fixation as one of above-mentioned characteristic
Property (especially shear stationarity and repel stationarity) on do not play sufficient performance, refer to so far acrylic acid series bonding
In agent composition presence can not being fixed property excellent adhesive tape the problem of.
Therefore, the present invention completes in view of the above problems, being capable of the excellent bonding of being fixed property its object is to provide
The acrylic adhesive composition of band.
For solving the means of technical problem
In order to solve the above-mentioned technical problem further investigation is repeated in the present inventor etc., as a result find：By using third
Polymer based on the ABA type triblock copolymer of olefin(e) acid system, have at least a portion use of the triblock copolymer
As the compound of the acrylic acid-2-ethyl caproite of segment B composition monomer, and make to contain in the base polymer using containing
There is the adhesive composition of the polymeric blends of regulation tackifying resin, it is hereby achieved that the adhesive tape that stationarity is excellent.Base
The present invention is completed in the opinion.
That is, the present invention is a kind of adhesive composition, and it contains：
The ABA type three block of segment B comprising the segments A based on methacrylate and based on acrylate
Copolymer (a),
The ABA type three block of segment B comprising the segments A based on methacrylate and based on acrylate
Copolymer (b) and
With above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b) have the softening point of compatibility for 110 DEG C with
On tackifying resin (c),
The adhesive composition has structure of the acrylic acid-2-ethyl caproite as the segment B of above-mentioned triblock copolymer (b)
Into monomer, above-mentioned triblock copolymer (b) is total relative to above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b)
The match ratio of amount is more than 0.1 mass % and below 50 mass %.
In above-mentioned adhesive composition, the weight average molecular weight of above-mentioned triblock polymer (a) is preferably 60, more than 000
And less than 400,000.
In above-mentioned adhesive composition, by the total amount of above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b)
When being set to 100 mass parts, the use level of above-mentioned tackifying resin (c) is preferably more than 15 mass parts and below 40 mass parts.
In above-mentioned adhesive composition, the segment B of above-mentioned triblock copolymer (b) composition monomer is preferably acrylic acid
N-butyl and acrylic acid-2-ethyl caproite.
Now, the n-butyl acrylate (BA) in the segment B of above-mentioned triblock copolymer (b) and acrylic acid-2-ethyl oneself
The match ratio of ester (2EHA) is preferably BA: 2EHA=75: 25~5: 95 by quality ratio.
Above-mentioned adhesive composition can also contain and above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b)
Softening agent (d) with compatibility.
Now, above-mentioned softening agent (d) is preferably selected from same with the segments A and segment B of above-mentioned triblock copolymer (a)
One kind or two or more compound in the AB types diblock copolymer of the segment of sample, acrylic compounds oligomer and liquid rubber.
In addition, above-mentioned tackifying resin (c) is preferably rosin series resin.
In addition, the present invention is a kind of adhesive tape, it is coated with above-mentioned adhesive composition at least one side of base material.
Invention effect
According to the present invention, by using polymer based on the acrylic acid series triblock copolymer with regulation structure,
And the adhesive composition for making the polymeric blends containing regulation tackifying resin in the base polymer using containing, thus
Can the excellent adhesive tape of being fixed property.
Embodiment
Hereinafter, the suitable embodiment of the present invention is described in detail.
It is explained, the adhesive composition of the present invention is illustrated according to following order.
The composition of 1 adhesive composition
1-1 triblock copolymers (a)
1-2 triblock copolymers (b)
1-3 tackifying resins (c)
1-4 any conditions
The form of 2 adhesive compositions
The purposes of 3 adhesive compositions
The composition of adhesive compositions
The adhesive composition of the present invention be containing polymer based on 2 kinds of ABA type triblock copolymers (a) and (b),
But also at least contain the composition of tackifying resin (c), in addition to bonding force, viscosity, the characteristic of confining force, above-mentioned stationarity
It is excellent.Hereinafter, each composition in the adhesive composition of the present invention is illustrated successively.
<Triblock copolymer (a)>
Triblock copolymer (a) is comprising the segments A based on methacrylate and based on acrylate
Segment B ABA type triblock copolymer.Here, " segment " described in the present invention refers to form respectively in triblock copolymer
The construction unit of block, for example, in construction unit (polymer or oligomer) A, the structure list comprising monomer b comprising monomer a
The ABA type that member (polymer or oligomer) B and construction unit (polymer or oligomer) A comprising monomer a are combined into successively
In the case of triblock copolymer, it is (also same in triblock copolymer (b) described later that construction unit A, B respectively become segments A, B
Sample).
(segments A)
As the segments A of triblock copolymer (a), as long as the chain for the main body for being formed monomer is used as using methacrylate
Section, then be not particularly limited, as such a methacrylate, can enumerate such as methyl methacrylate, methacrylic acid second
The secondary butyl ester of ester, isopropyl methacrylate, methacrylic acid, Isobutyl methacrylate, Tert-butyl Methacrylate, methyl-prop
Olefin(e) acid cyclohexyl, isobornyl methacrylate, methacrylic acid 1- methyl cyclohexyls, methacrylic acid 2- methyl cyclohexyls,
Methacrylic acid 3- methyl cyclohexyls, methacrylic acid 4- methyl cyclohexyls, methacrylic acid 2- phenoxy ethyls, metering system
Sour 2- methoxy acrylates, methacrylic acid 2- (N, N- dimethylamino) ethyl ester, methacrylic acid trifluoromethyl ester, methacrylic acid are just
Pentyl ester, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, lauryl methacrylate, methacrylic acid ten
Trialkyl ester, stearyl methacrylate, methacrylic acid 2- methoxyl groups pentyl ester, methacrylic acid 2- (N, N- dimethylamino) penta
Ester, methacrylic acid perfluor pentyl ester, methacrylic acid 2- trimethoxysilyl pentyl esters etc..
In above-mentioned monomer, in order to improve the adhesion characteristic (especially in the confining force of high temperature) of bonding adjuvant, as
Segments A composition monomer main body, preferably using methyl methacrylate, EMA, n propyl methacrylate,
The monomers such as the ester that alcohol of the methacrylic acids such as isopropyl methacrylate with carbon number below 3 is formed.
Here, in order to can be described as heretofore described " as main body ", preferably with the composition of monomer than (mass ratio)
Meter contains more than 50%, further preferably more than 80%, further preferably more than 90%.
In addition, for the composition monomer of the segments A of triblock copolymer (a), as except above-mentioned methacrylate
The monomer that can be used in addition, can be enumerated for example：Methacrylamide, N- methyl methacrylamides, N- ethyl-methyls third
The first such as acrylamide, N- isopropyl acrylamides, N, N- dimethylmethacryl amides, N, N- diethyhnethacrylamides
Base acrylic amide；Acrylamide, N methacrylamide, N- ethyl acrylamides, NIPA, N, N- diformazans
The acrylic amide such as base acrylamide, N, N- acrylamides；Methacrylic acid, acrylic acid, crotonic acid, maleic acid, horse
Coming acid anhydrides, fumaric acid etc. has the vinyl monomer of carboxyl；The fragrance such as styrene, α-methylstyrene, p-methylstyrene
Race's vinyl monomer；Butadiene, isoprene equiconjugate diene monomer；The alkene such as ethene, propylene；6-caprolactone, in penta
Lactones such as ester etc..
(segment B)
Then, the segment B as triblock copolymer (a), as long as the main body for being formed monomer is used as using acrylate
Segment, then it is not particularly limited, as such a acrylate, such as methyl acrylate, ethyl acrylate, acrylic acid can be being enumerated just
Propyl ester, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid
Just own ester, lauryl ester, acrylic acid tridecane ester, stearyl acrylate ester, cyclohexyl acrylate, isobomyl acrylate
Ester, acrylic acid 2- methoxy acrylates, acrylic acid 2- (N, N- dimethylamino) ethyl ester, acrylic acid trifluoromethyl ester, acrylic acid front three
Epoxide silicyl propyl ester, lauryl acrylate, acrylic acid 2- methylbutyl butenoates, acrylic acid 4- methyl -2- pentyl esters, acrylic acid are just pungent
Ester, Isooctyl acrylate monomer, acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters etc..
In addition, for the segment B of triblock copolymer (a) composition monomer, as in addition to above-mentioned acrylate
The monomer that can be used, can enumerate for example：Alkyl methacrylate (such as methyl methacrylate, methacrylic acid second
The secondary butyl ester of ester, isopropyl methacrylate, methacrylic acid, Isobutyl methacrylate, Tert-butyl Methacrylate, methyl-prop
Olefin(e) acid cyclohexyl, other as above-mentioned segments A composition monomer methyl acrylic ester)；Methacrylamide, N- methyl first
Base acrylamide, N- ethyl methacrylamides, N- isopropyl acrylamides, N, N- dimethylmethacryl amides, N,
The methacryl amine such as N- diethyhnethacrylamides；Acrylamide, N methacrylamide, N- ethyl acrylamides,
The acrylic amide such as NIPA, N,N-DMAA, N, N- acrylamides；Metering system
Acid, acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid etc. have the vinyl monomer of carboxyl；Styrene, adjacent methyl
The aromatic vinyl base system monomer such as styrene, p-methylstyrene；Butadiene, isoprene equiconjugate diene monomer；Ethene,
The alkene such as propylene；Lactones such as 6-caprolactone, valerolactone etc..
(weight average molecular weight)
The adhesive composition of the present invention has excellent stationarity, weight of the stationarity by triblock copolymer (a)
The influence of average molecular weight.Specifically, the weight average molecular weight of triblock copolymer (a) is preferably 60, more than 000 and 400,000
Below.If the weight average molecular weight of triblock copolymer (a) is less than 60,000, then the not only bonding force of adhesive composition, cohesion
The general characteristics such as power, viscosity reduce, and stationarity also reduces, therefore not preferred.In order to further improve above-mentioned characteristic, three
The weight average molecular weight of block copolymer (a) is more preferably 110, more than 000, more preferably 130, and more than 000, particularly preferably
For more than 150,000.On the other hand, due to needing with the mobility for being suitable for melt-shaping, therefore triblock copolymer (a)
Weight average molecular weight be preferably less than 400,000.In order to further improve above-mentioned effect, the weight of triblock copolymer (a) is equal
Molecular weight is more preferably less than 300,000.
It is explained, as the weight average molecular weight in the present invention, using by utilizing the poly- of gel permeation chromatography (GPC) measure
The value that styrene conversion molecular weight is tried to achieve.
(hard segment contents)
Using the gross mass of triblock copolymer (a) as benchmark, the content of the hard segment in triblock copolymer (a) is preferred
For 5~30 mass %, more preferably 5~25 mass %, particularly preferably 10~20 mass %.
(preparation method)
As the triblock copolymer (a) of the present invention, city can also be used by synthesizing starting monomer polymerization
The product sold.As polymerization, there is no particular restriction, such as anionic polymerization, atom freedom of movement base can be used to gather
Legal (ATRP) etc..The detailed description to each polymerization is omitted herein, as anionic polymerization, can be used for example with organic
Alkali metal compound carry out as polymerization initiator and in the presence of the inorganic acid salts such as the salt of alkali metal or alkaline-earth metal it is cloudy from
The method of son polymerization, carry out using organic alkali metal compound as polymerization initiator and in the presence of organo-aluminum compound the moon from
The method of son polymerization, using organic RE metalloid complex compound as polymerization initiator known to method etc. of progress anionic polymerisation
Method, as ATRP, it can use for example using organohalogen compounds or sulfonyl halide based compound as initiator and in transition gold
Method known to method being polymerize in the presence of category compound, nitrogen-containing compound etc..As commercially available product, it can enumerate and for example may be used
" CLARITY (registration mark) series " of happy beautiful (strain) system etc..
<Triblock copolymer (b)>
Triblock copolymer (b) is similarly comprising the segments A based on methacrylate with triblock copolymer (a)
With the ABA type triblock copolymer of the segment B based on acrylate.But with acrylic acid-2-ethyl caproite conduct
The aspect of segment B composition monomer, triblock copolymer (b) have the structure different from triblock copolymer (a).
The adhesive composition of the present invention also coordinates in addition to above-mentioned triblock copolymer (a) has Tg fourths more positive than acrylic acid
Copolymer (b) of the lower acrylic acid-2-ethyl caproite of ester as the composition monomer of the segment B in ABA type three block, so as to remove
Bonding force, viscosity, confining force these to stationarity can also be significantly improved outside characteristic generally required for adhesive.Enable in particular to show
Write improve as with triblock copolymer (b) bring it is effect, will attaching thing (such as the stationery such as ground paper) be fixed as
Tubular isotactic setting shape caused by be such as resistant to want to return to original form repulsive force (attach thing do not shell each other
From) characteristic (repulsion stationarity).Hereinafter, triblock copolymer (b) is described in detail.
(segments A)
The segments A of triblock copolymer (b) is same with the segments A of above-mentioned triblock copolymer (a), therefore omits herein
Detailed description thereof.It is explained, in the adhesive composition of the present invention, the segments A of triblock copolymer (a) and three embedding
The segments A of section copolymer (b) can be identical segment, or different segments, still, if considering triblock copolymer
(a) with the compatibility of triblock copolymer (b), then preferably make both segments As identical.
(segment B)
The segment B of triblock copolymer (b), which needs to be used as with acrylic acid-2-ethyl caproite as described above, forms monomer,
Can also have " others form monomer ".As " others form monomer " now, can use can be used as three block
The monomer that the segment B of copolymer (a) composition monomer uses.Wherein, go out in terms of the compatibility with triblock copolymer (a)
Hair, as " others form monomer ", preferably using n-butyl acrylate.That is, the segment B of triblock copolymer (b) composition
Monomer is preferably n-butyl acrylate and acrylic acid-2-ethyl caproite.
Alternatively, it is also possible to use composition monomer of the n-butyl acrylate as segment B.The segment B of triblock copolymer (b)
In the match ratio of n-butyl acrylate (BA) and acrylic acid-2-ethyl caproite (2EHA) be preferably BA: 2EHA by quality ratio
=95: 5~0: 100.By making match ratio be the scope, so that fixed raising effect of adhesive composition uprises.
In order to further improve fixed raising effect, preferably make 2EHA match ratio higher, specifically, more preferably BA:
2EHA=75: 25~5: 95, more preferably 60: 40~5: 95.
It is explained, in the adhesive composition of the present invention, " other compositions in the segment B of triblock copolymer (b)
Monomer " can be with identical with the segment B of triblock copolymer (a) composition monomer, can also be different, still, if considering three block
The compatibility of copolymer (a) and triblock copolymer (b), then preferably make both composition single phases same.
(weight average molecular weight)
From practicality, from the viewpoint of stably manufacture, the triblock copolymer (b) in adhesive composition of the invention
Weight average molecular weight preferred scope be more than 30,000 and less than 200,000, more preferably less than 150,000.If weight average molecular weight is less than 3
Ten thousand, then bonding force is too low, problem in practical be present, if weight average molecular weight, more than 200,000, viscosity is too high, therefore in manufacture
Problem be present.
It is explained, as the weight average molecular weight in the present invention, using by utilizing the poly- of gel permeation chromatography (GPC) measure
The value that styrene conversion molecular weight is tried to achieve.
(hard segment contents)
Using the gross mass of triblock copolymer (b) as benchmark, the content of the hard segment in triblock copolymer (b) is preferred
For 10~40 mass %, more preferably 15~30 mass %, particularly preferably 20~25 mass %.
(preparation method)
As the triblock copolymer (b) of the present invention, city can also be used by synthesizing starting monomer polymerization
The product sold.As polymerization, there is no particular restriction, and the concrete example and triblock copolymer (a) of polymerization are same.As city
Product are sold, can be enumerated such as " CLARITY (registration mark) series " that Kuraray (strain) is made.
(match ratio of triblock copolymer (a) and triblock copolymer (b))
The present invention adhesive composition in, in order to effectively embody stationarity, it is necessary to make triblock copolymer (a) with
(triblock copolymer (b) is relative to triblock copolymer (a) and triblock copolymer (b) for the match ratio of triblock copolymer (b)
Total amount match ratio) be more than 0.1 mass %.Thus, uprise fixed raising significant effect of adhesive composition.
On the other hand, if the match ratio of triblock copolymer (b) is too high, based on the performance of polymer reduce, therefore not only glue
With joint efforts, the general characteristic such as viscosity, confining force reduces, and the stationarity of adhesive composition also reduces.It is therefore preferable that make three embedding
The match ratio of section copolymer (a) uprises.In particular, it is desirable to the match ratio for making triblock copolymer (b) is below 50 mass %.
In order to further improve fixed raising effect, the lower limit of the use level of triblock copolymer (b) be preferably 1 mass % with
On, more preferably more than 3 mass %, more preferably more than 5 mass %, particularly preferably more than 10 mass %.The opposing party
Face, in order to further improve fixed raising effect and suppress the reduction of general characteristic, triblock copolymer (b) is matched somebody with somebody
The higher limit of resultant is preferably below 40 mass %, more preferably below 30 mass %, particularly preferably below 20 mass %.
<Tackifying resin (c)>
The adhesive composition of the present invention is except above-mentioned base polymer beyond the region of objective existence also containing tackifying resin (c) as must be into
Point.Can only have by above-mentioned triblock copolymer (a) and triblock copolymer (b) and be used as general adhesive composition
Function, but bonding force is low, and it is impracticable.Therefore, adhesive composition of the invention is by containing tackifying resin (c), from
And bonding force is improved to sufficient level in practical, and meet bonding force, viscosity, confining force these as adhesive
General characteristic.
(compatibility with triblock copolymer)
Here, tackifying resin (c) is that have compatibility with triblock copolymer (a) and triblock copolymer (b) so as to energy
Enough and triblock copolymer (a) and triblock copolymer (b) form the resin of polymeric blends.There is compatibility as such a
Resin, there is no particular restriction, can use such as rosin series, terpenic series.As rosin series resin, such as rosin can be enumerated
Ester, hydrogenated wood rosin glycerol ester, rosin ester, newtrex ester, gum rosin (gum rosin), Starex, maleic rosin are not homogenized
(Maleated rosin), maleic acid modified rosin etc., as terpenic series resin, such as terpene phenolic resin, hydrogenation can be enumerated
Terpene phenolic resin, aromatic modified terpene resin, aromatic modified hydrogenated terpene resin hydrogenated terpene resin, with australene,
Nopinene, limonene etc. are the terpenic series resin of main body.Wherein, from the viewpoint of stationarity is improved, the increasing as the present invention
Viscosity resin, preferably using rosin series resin.
(softening point)
In addition, the tackifying resin (c) as the present invention, uses the tackifying resin that at least one kind of softening point is more than 100 DEG C.
By coordinating the high tackifying resin (c) of such a softening point, so as to except bonding force, viscosity, these institutes usual to adhesive of confining force
It is required that characteristic outside can also significantly improve stationarity.Especially, by coordinating high (more than the 100 DEG C) tackifying resin of softening point
(c), so as to significantly improve will attach thing (such as the stationery such as picture poster) be attached at as defined in by attaching face (such as wall
Face) caused by be such as resistant to stress, the vertical direction as caused by gravity caused by relaxation or warpage as attaching thing
(attaching thing not peel off from by the face of attaching) characteristic (shearing stationarity) of shearing force.Go out from the viewpoint for further improving the characteristic
Hair, the softening point of tackifying resin (c) is preferably more than 110 DEG C, more preferably more than 120 DEG C.
On the other hand, if the softening point of tackifying resin (c) is too high, resin becomes really up to the mark, can not obtain being suitable as gluing
The viscosity of mixture.Therefore, the softening point of tackifying resin (c) is preferably less than 200 DEG C, is more preferably less than 170 DEG C, is further excellent
Elect less than 165 DEG C as, be most preferably less than 160 DEG C.Additionally, it is preferred that based on the tackifying resin with above-mentioned preferred softening point
Want composition (being more than 50 mass % using the gross mass of whole tackifying resins as benchmark).
(use level)
When the total amount of triblock copolymer (a) and above-mentioned triblock copolymer (b) is set into 100 mass parts, thickening tree
The use level of fat (c) is preferably more than 15 mass parts and below 40 mass parts.If the use level of tackifying resin (c) is less than 15 mass
Part, then become insufficient risk in the presence of its additive effect (bonding force or fixed raising effect).From significantly more improving
From the viewpoint of the bonding force of adhesive composition, stationarity, the use level of tackifying resin (c) be more preferably 25 mass parts with
On.On the other hand, if the use level of tackifying resin (c) has the risk that viscosity reduces more than 40 mass parts.
<Any condition：Softening agent (d)>
The present invention adhesive composition except above-mentioned base polymer beyond the region of objective existence can also containing softening agent (d) as it is any into
Point.Only there can be the adhesive for being used as the present invention to combine by above-mentioned triblock copolymer (a) and triblock copolymer (b)
The function of thing, but bonding force is low, and it is sometimes insufficient in practical.Therefore, adhesive composition of the invention by containing
Have softening agent (d), so that bonding force is improved to sufficient level in practicality, and meet bonding force, viscosity, confining force these
General characteristic as adhesive.
(compatibility with triblock copolymer)
Here, softening agent (d) be there is compatibility with triblock copolymer (a) and triblock copolymer (b) so as to
The resin of polymeric blends is formed with triblock copolymer (a) and triblock copolymer (b).As such a with compatibility
Compound, there is no particular restriction, can enumerate the segment same for example with the segments A with triblock copolymer (a) and segment B
AB types diblock copolymer, acrylic polymer, acrylic compounds oligomer, liquid rubber (such as polybutene, polyisobutene,
Polyisoprene), technical oil, phthalate, adipic acid esters, sebacic acid ester, aliphatic ester, polyethers etc..
These compounds can be used alone, and can also be applied in combination two or more.In these compounds, it is total to from three block
Polymers (a) and the good aspect of triblock copolymer (b) compatibility are set out, be particularly preferably used alone diblock copolymer or
Diblock copolymer and acrylic compounds oligomer is applied in combination.
As above-mentioned diblock copolymer, the segments A and segment B as long as there is above-mentioned triblock copolymer (a) are same
Segment, then be not particularly limited.But if consider softening agent (d) and triblock copolymer (a) and triblock copolymer (b)
Compatibility, then preferably make diblock copolymer segments A and B respectively comprising segments A and B phases with triblock copolymer (a)
Same composition monomer.Now, in order that compatibility highest, is preferably：The composition monomer of the segments A of triblock copolymer (b)
It is identical with the segments A of diblock copolymer and triblock copolymer, the segment B of triblock copolymer (b) above-mentioned " other compositions
Monomer " is identical with the segment B of diblock copolymer and triblock copolymer.In addition, in order that with triblock copolymer (a) and three
The compatibility of block copolymer (b) uprises, and it is preferred that aforesaid propylene acid based oligomerization thing, liquid rubber.
(use level)
From the viewpoint of the viscosity for improving adhesive composition, softening agent (d) can be coordinated.By triblock copolymer
(a) when being set to 100 mass parts with the total amount of above-mentioned triblock copolymer (b), the use level of softening agent (d) is preferably 250 mass
Below part.If the use level of softening agent (d), more than 250 mass parts, presence causes what the confining force of adhesive composition reduced
Possibility.Therefore, in order to improve stationarity, more preferably below 200 mass parts, more preferably below 150 mass parts.Separately
Outside, lower limit is not particularly limited, for example, 50 mass parts.
<Any condition：Other>
In addition, the present invention adhesive composition in can add in the range of effect of the present invention is not hindered one kind or
Two or more filler, antioxidant, heat stabilizer, ultra-violet absorber, light stabilizer, antistatic additive, fire retardant, foaming
Other additives such as agent, colouring agent, coloring agent.
《The form of adhesive composition》
More than, the composition of the adhesive composition of the present invention is explained, still, the adhesive composition
Can also be make above-mentioned triblock copolymer (a), triblock copolymer (b), tackifying resin (c), softening agent (d) and arbitrarily into
Divide (binder materials) to be dissolved in the solvent-based adhesive composition that regulation solvent forms, can also be to make above-mentioned binder materials
The hot-melt adhesive composition for melting and being kneaded.It is explained, as the used solvent in the case of solution-type,
The organic solvent such as toluene, ethyl acetate can be used.
《The purposes of adhesive composition》
The adhesive composition of present invention mentioned above can be used for the purposes such as adhesive tape (one or two sides).Hereinafter,
As one of the purposes of the adhesive composition of the present invention, the adhesive composition above-mentioned to the two sided coatings in base material forms
Double-sided adhesive tape illustrate.It is explained, in the case of single-sided adhesive tape, except the one side coating adhesive in base material
In addition, and equally.
Combined using the double-sided adhesive tape of the adhesive composition of the present invention in the above-mentioned adhesive of the two sided coatings of base material
Thing, and adhere to peeling paper as needed on the surface of adhesive composition.
As base material, as long as can the shape such as the membranaceous of coating adhesive composition, sheet, then there is no particular restriction,
It can use for example：The paper such as brown paper, Japan paper, crepe paper (crepe)；Comprising artificial silk, cotton, acetic acid esters, polyethylene (PE), poly-
The non-woven fabrics of propylene (PP) etc.；Cellophane (cellophane), vinyl chloride, PE, oriented polypropylene (OPP), poly terephthalic acid
The resin films such as glycol ester (PET), tetrafluoroethene, polyimides, makrolon (PC), polystyrene (PS)；Polyurethane, PE,
The foamed resins such as butyl rubber；The metal foils such as aluminium, copper；Sheet rubbers such as natural rubber, SBR, butyl rubber etc..
In addition, the method as the coating adhesive composition on base material, is also not particularly limited, can use make bonding
Method (molten exhibition method) that agent dissolution of raw material is coated again after organic solvent, make that its is thinning using multiple hot-rollings after (thin go out)
The method (rolling process) that is coated again, make known to method (hot melt) for being coated again after binder materials heat fusing etc.
Method.
Embodiment
Below, the present invention is further illustrated using embodiment and comparative example, but the present invention is not by these
Any restriction of example.
<The explanation of raw material>
Using following raw material, embodiment 1~27, the double-sided adhesive tape of comparative example 1~7 are made.
[triblock copolymer (a)]
Triblock copolymer (a-1)：Methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three block
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents are 16 mass %), molecular weight 140,
000
Triblock copolymer (a-2)：Methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three block
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents are 22 mass %), molecular weight 115,
000
Triblock copolymer (a-3)：Methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three block
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents are 23 mass %), molecular weight 75,
000
Triblock copolymer (a-4)：Methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three block
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents are 12 mass %), molecular weight 180,
000
[triblock copolymer (b)]
Triblock copolymer (b-1)：Methyl methacrylate-n-butyl acrylate -2-EHA (2EHA)
(three block body, hard segment MMA, soft chain segment are n-BA and 2EHA, n-BA to copolymer: 2EHA=50: 50 (mass ratioes), hard chain
Duan Hanliang is 23 mass %) molecular weight is 100,000
Triblock copolymer (b-2)：Methyl methacrylate-n-butyl acrylate -2-EHA (2EHA)
(three block body, hard segment MMA, soft chain segment are n-BA and 2EHA, n-BA to copolymer: 2EHA=20: 80 (mass ratioes), hard chain
Duan Hanliang is 23 mass %) molecular weight is 100,000
Triblock copolymer (b-3)：Methyl methacrylate-n-butyl acrylate -2-EHA (2EHA)
(three block body, hard segment MMA, soft chain segment are n-BA and 2EHA, n-BA to copolymer: 2EHA=80: 20 (mass ratioes), hard chain
Duan Hanliang is 23 mass %) molecular weight is 100,000
Triblock copolymer (b-4)：Methyl methacrylate -2-EHA (2EHA) copolymer (three block
Body, hard segment MMA, soft chain segment 2EHA, hard segment contents are 23 mass %) molecular weight be 80,000
[tackifying resin (c)]
Pensel A：Rosin ester (softening point is 100 DEG C)
Pensel D-125：Newtrex ester (softening point is 125 DEG C)
Pensel D-135：Newtrex ester (softening point is 135 DEG C)
Pensel D-160：Newtrex ester (softening point is 160 DEG C)
YS POLYSTAR G150：Terpene phenolic copolymer (softening point is 150 DEG C)
[softening agent (d)]
CLARITY LA1114：(diblock body, hard segment are methyl methacrylate-n-butyl acrylate copolymers
MMA, soft chain segment n-BA)
ARUFON (registration mark) UP-1000：Acrylic polymer without functional group's type
<Manufacture method>
Above-mentioned raw material are glued according to the use level (unit is mass parts) shown in table 1 below using molten exhibition legal system as two sides
Crossed belt.Specifically, above-mentioned raw material are added with the use level shown in table 1 below in toluene, stirring dissolves the raw material,
It is fabricated to solvent-based adhesive composition (solid component concentration is 50 mass %).Then, by the adhesive composition profit of gained
With applicator coated on peeling paper.After being dried 3 minutes in 100 DEG C of baking oven, non-woven fabrics (I) and adhesive composition are pasted
Close.Then, adhesive composition is applied on peeling paper as described above, after drying, is bonded with the non-woven fabrics side of (I), is made
Make double-sided adhesive tape.The coating weight on the two sides of adhesive composition is set to 25g/m2.Finally, in order that adhesive and non-woven fabrics
Grappling (anchoring) well, and implement 120 DEG C of heat lamination, the two sides for making embodiment 1~27 and comparative example 1~7 is glued
Crossed belt.
<Evaluation method>
For the embodiment 1~27 and the double-sided adhesive tape of comparative example 1~7 made in the manner described above, using following
Method carries out the evaluation of each characteristic.
(1) fundamental characteristics (SUS bonding forces, probe tack, ball viscosity, glass confining force)
On fundamental characteristics, it is determined according to JIS Z 0237.But in the evaluation of SUS bonding forces, as examination
Test plate and compression bonding method, using from JIS Z 0237 specified in the different method of method.Specifically, in SUS bonding forces
In evaluation, as breadboard, reused after SUS304 steel plates specified in JIS G 4305 are completed into surface grinding.In addition,
During crimping, 2000g roller is set to place 20~40 minutes after crimping, afterwards, determine with reciprocal 1 time of the speed of 300mm/ minutes
Bonding force (other are same with JIS Z 0237).
(2) stationarity experiment is sheared
In A2 sizes, weight per unit area 87g/m2, 125 μm of thickness ASKUL color coatings paper (picture poster) corner patch
The double-sided adhesive tape of attached 15mm square.Afterwards, color coating paper strength is pressed and attached to finger and be pasted with SANGETSU chlorine
On ethene wallpaper SP7204 wall, placed more than 12 hours in the environment of 40 DEG C, about 10%RH.Now, picture poster is measured
From the fall time after attaching untill being fallen from wall, evaluated according to following benchmark.
A：Fall time is more than 4 days
B：Fall time was more than 24 hours and less than 4 day
C：Fall time was more than 5 hours and less than 24 hour
D：Fall time was less than 5 hours
(3) stationarity experiment is repelled
With A4 sizes, weight per unit area 500g/m2Modern village's paper work making sheet mesh table paper (ground paper) short side one end pair
The wide double-sided adhesive tapes of 15mm are attached together, are rolled ground paper along diameter 78mm paper tube, are bonded, are made with the short side of the other end
Cylinder.Now, measure from the splitting time after attaching untill cylinder is opened and (peeled off the fitting part of ground paper), according to following
Benchmark is evaluated.
A：Splitting time is more than 6 days
B：Splitting time was more than 24 hours and less than 6 day
C：Splitting time was more than 5 hours and less than 24 hour
D：Splitting time was less than 5 hours
<Evaluation result>
Understand：By also adding PMMA/Pn-BA-2EHA/PMMA except PMMA/Pn-BA/PMMA triblock copolymer beyond the region of objective existences, from
And make such as to be fixed as can be resistant to as the paper work of tubular by ground paper in the state of bonding force, viscosity and confining force is maintained
The repulsion stationarity for the repulsive force peeled off significantly improves.It is explained, on fundamental characteristics, in embodiment 1, SUS bondings
Power is 7.6 [N/15mm], and probe tack is 9.3 [N/5mm φ], and ball viscosity is No.12, and glass confining force is 0.2 [mm/15
20·1kg·1h].In addition, in other embodiments and comparative example, the result substantially equal with embodiment 1 is obtained.
In addition, understand：The tackifying resin high by adding softening point, so as to also make such as to paste a surname in addition to stationarity is repelled
Stress caused by relaxation or the warpage as paper is resistant to as biography picture, the shearing force of vertical direction cuts as caused by gravity
Cut stationarity raising.
[table 1]
【Table 1】
[table 2]
【Table 2】
[table 3]
【Table 3】
More than, the preferred embodiment of the present invention is illustrated, but the present invention is not limited by above-mentioned embodiment
It is fixed.I.e., it is possible to be interpreted as claims record invention in the range of those skilled in the art it is conceivable that other realities
Apply mode or various modifications example is fallen within the technical scope of the present invention.
Claims (7)
1. a kind of adhesive composition, it contains：
The ABA type triblock copolymer of segment B comprising the segments A based on methacrylate and based on acrylate
Thing (a),
The ABA type triblock copolymer of segment B comprising the segments A based on methacrylate and based on acrylate
Thing (b) and
It it is more than 110 DEG C with the softening point of the triblock copolymer (a) and the triblock copolymer (b) with compatibility
Tackifying resin (c),
As the segment B of the triblock copolymer (b) composition monomer, there is acrylic acid-2-ethyl caproite,
As the segment B of the triblock copolymer (a) composition monomer, without acrylic acid-2-ethyl caproite,
The triblock copolymer (b) is relative to the total amount of the triblock copolymer (a) and the triblock copolymer (b)
Match ratio is more than 0.1 mass % and below 50 mass %,
When the total amount of the triblock copolymer (a) and the triblock copolymer (b) is set into 100 mass parts, the increasing
The use level of viscosity resin (c) be 15 mass parts more than,
The weight average molecular weight of the triblock copolymer (a) is 60, more than 000 and 400, less than 000, the triblock copolymer
(b) weight average molecular weight is more than 30,000 and less than 200,000.
2. adhesive composition according to claim 1, wherein, by the triblock copolymer (a) and the three block
When the total amount of copolymer (b) is set to 100 mass parts, the use level of the tackifying resin (c) is more than 15 mass parts and 40 mass
Below part.
3. adhesive composition according to claim 1, wherein, the segment B of the triblock copolymer (b) composition list
Body is n-butyl acrylate and acrylic acid-2-ethyl caproite.
4. adhesive composition according to claim 3, wherein, the propylene in the segment B of the triblock copolymer (b)
Sour N-butyl, i.e. BA and acrylic acid-2-ethyl caproite, i.e. 2EHA match ratio are BA by quality ratio：2EHA=75：25~
5：95.
5. adhesive composition according to claim 1, it also contains and the triblock copolymer (a) and described three embedding
Section copolymer (b) has the softening agent (d) of compatibility.
6. adhesive composition according to claim 5, wherein, the softening agent (d) be selected from with it is described three embedding
Diblock copolymer, acrylic compounds oligomer and the liquid of the segments A of section copolymer (a) and the AB types of the same segments of segment B
One kind or two or more compound in rubber.
7. a kind of adhesive tape, it is coated with adhesive combination according to any one of claims 1 to 6 at least one side of base material
Thing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-011037 | 2014-01-24 | ||
| JP2014011037 | 2014-01-24 | ||
| PCT/JP2015/051627 WO2015111646A1 (en) | 2014-01-24 | 2015-01-22 | Acrylic pressure-sensitive-adhesive composition and pressure-sensitive-adhesive tape |
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| Publication Number | Publication Date |
|---|---|
| CN105829479A CN105829479A (en) | 2016-08-03 |
| CN105829479B true CN105829479B (en) | 2017-12-29 |
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| CN201580003157.2A Active CN105829479B (en) | 2014-01-24 | 2015-01-22 | Acrylic adhesive composition and adhesive tape |
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| Country | Link |
|---|---|
| JP (1) | JP6431854B2 (en) |
| KR (1) | KR102228806B1 (en) |
| CN (1) | CN105829479B (en) |
| WO (1) | WO2015111646A1 (en) |
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| CN106661410A (en) * | 2014-08-20 | 2017-05-10 | 株式会社可乐丽 | Acrylic adhesive composition and adhesive product |
| JP2016141725A (en) * | 2015-01-30 | 2016-08-08 | リンテック株式会社 | Adhesive tape |
| CN105885746A (en) * | 2016-05-04 | 2016-08-24 | 广州市豪特粘接材料有限公司 | Hot melt adhesive for PVC (polyvinyl chloride)/metal bonding and preparation method thereof |
| JP6897334B2 (en) * | 2017-05-31 | 2021-06-30 | 王子ホールディングス株式会社 | Adhesive sheet |
| JP2017214596A (en) * | 2017-08-30 | 2017-12-07 | 株式会社クラレ | Adhesive composition |
| JP2018003034A (en) * | 2017-10-16 | 2018-01-11 | 株式会社クラレ | Pressure-sensitive adhesive composition |
| CN113227288B (en) * | 2018-12-27 | 2022-08-02 | 株式会社可乐丽 | Laminate having structure body including through-hole |
| CN113402685B (en) * | 2021-05-26 | 2022-04-22 | 华南理工大学 | Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1824719A (en) * | 2005-01-25 | 2006-08-30 | 国誉S&T株式会社 | Adhesive product and transferring instrument |
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| JP5051967B2 (en) | 2004-04-23 | 2012-10-17 | 株式会社クラレ | Acrylic block copolymer composition |
| JPWO2007029783A1 (en) * | 2005-09-07 | 2009-03-19 | 株式会社クラレ | Acrylic adhesive composition and adhesive product |
| WO2008065982A1 (en) * | 2006-12-01 | 2008-06-05 | Kuraray Co., Ltd. | Pressure-sensitive adhesive for optical films |
| JP5296364B2 (en) | 2007-10-22 | 2013-09-25 | 三菱樹脂株式会社 | Acrylic transparent adhesive composition |
| JP2011028069A (en) * | 2009-07-28 | 2011-02-10 | Kuraray Co Ltd | Method for producing adhesive optical film |
| CA2870435A1 (en) * | 2012-04-27 | 2013-10-31 | Kuraray Co., Ltd. | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive products |
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| CN1824719A (en) * | 2005-01-25 | 2006-08-30 | 国誉S&T株式会社 | Adhesive product and transferring instrument |
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| CN105829479A (en) | 2016-08-03 |
| KR20160113159A (en) | 2016-09-28 |
| JPWO2015111646A1 (en) | 2017-03-23 |
| WO2015111646A1 (en) | 2015-07-30 |
| KR102228806B1 (en) | 2021-03-18 |
| JP6431854B2 (en) | 2018-11-28 |
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