CN105829479A - Acrylic adhesive composition and adhesive tape - Google Patents
Acrylic adhesive composition and adhesive tape Download PDFInfo
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- CN105829479A CN105829479A CN201580003157.2A CN201580003157A CN105829479A CN 105829479 A CN105829479 A CN 105829479A CN 201580003157 A CN201580003157 A CN 201580003157A CN 105829479 A CN105829479 A CN 105829479A
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- Prior art keywords
- triblock copolymer
- segment
- adhesive composition
- copolymer
- mass
- Prior art date
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Classifications
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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
- 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 invention provides an acrylic adhesive composition and an adhesive tape. To provide an adhesive composition whereby an adhesive tape having excellent fixing properties can be obtained. The adhesive composition contains an ABA-type triblock copolymer (a) comprising a segment (A) having a methacrylic acid ester as the main component thereof and a segment (B) having an acrylic acid ester as the main component thereof, an ABA-type triblock copolymer (b) comprising a segment (A) having a methacrylic acid ester as the main component thereof and a segment (B) having an acrylic acid ester as the main component thereof, and a tackifying resin (c) compatible with the triblock copolymer (a) and the triblock copolymer (b) and having a softening point of 110 DEG C or above, the segment (B) of the triblock copolymer (b) having 2-ethylhexyl acrylate as a constituent monomer, and the triblock copolymer (b) being blended in a ratio of 0.1% by mass to 50% by mass with respect to the total amount of the triblock copolymer (a) and the triblock copolymer (b).
Description
Technical field
The present invention relates to a kind of adhesive composition, more specifically, relate to a kind of acrylic adhesive composition and
This adhesive composition is coated the adhesive tape of base material.
Background technology
Containing the acrylic adhesive of (methyl) acrylic ester monomer have weatherability, the transparency, thermostability,
Solvent resistances etc. are excellent and can easily control the advantage of bonding force by changing the composition of the monomer constituted, therefore
Carry out the most energetically studying (referring for example to Japanese documentation 1～3).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-307063 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-102467 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-206624 publication
Summary of the invention
Invention to solve the technical problem that
Here, as generally to the representational practical characteristic required by adhesive tape, can enumerate bonding force (peel strength),
Viscosity (cohesive) and three fundamental characteristics of retentivity (cohesiveness), the purposes according to adhesive tape is different, except above-mentioned fundamental characteristics
Outward, this characteristic of stationarity is the most also required.As this kind of fixed example, can enumerate such as: (such as declare thing will be attached
Pass the stationery such as picture) be attached at regulation produced time attaching face (such as wall) be such as resistant to by attach the lax of thing or
Stress that warpage produces, the shearing force of vertical direction produced by gravity (attaching thing not peel off from by attaching face) characteristic (with
Under, it is recited as " shearing stationarity ".)；Or, when thing stationeries such as () such as ground paper will be attached will be fixed as tubular isotactic shaped
(the attaching thing not peel off) characteristic of the repulsive force being such as resistant to want to return to original form produced (below, is recorded
For " repulsion stationarity ".) etc..That is, stationarity said here refers to: and the characteristic of non-adhesive itself, but be resistant to
The regulation external force such as above stress, gravity, repulsive force (even if attaching also can be maintained in the case of applying regulation external force
Have the state attaching thing) characteristic.
For the acrylic adhesive composition described in above-mentioned patent documentation 1～3, although current situation be with
Practical level has as above to the fundamental characteristics required by adhesive tape, but fixing as one of above-mentioned characteristic
Property (especially shear stationarity and repel stationarity) on do not play sufficient performance, mention so far acrylic acid series bonding
Agent compositions exists the problem that cannot obtain the excellent adhesive tape of stationarity.
To this end, the present invention completes in view of the above problems, its object is to provide the bonding that can obtain stationarity excellence
The acrylic adhesive composition of band.
For solving the means of technical problem
The present inventor etc. are repeated further investigation to solve above-mentioned technical problem, found that: by using third
Polymer based on the ABA type triblock copolymer of olefin(e) acid system, at least some of use at this triblock copolymer has
As the compound of the acrylic acid-2-ethyl caproite constituting monomer of segment B, and use containing making this base polymer contains
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 this opinion.
That is, the present invention is a kind of adhesive composition, and it contains:
Comprise ABA type three block of the segments A based on methacrylate and the segment B based on acrylate
Copolymer (a),
Comprise ABA type three block of the segments A based on methacrylate and the segment B based on acrylate
Copolymer (b) and
With above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b) have the softening point of the compatibility be 110 DEG C with
On tackifying resin (c),
This adhesive composition has the acrylic acid-2-ethyl caproite structure as the segment B of above-mentioned triblock copolymer (b)
Becoming 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 below more than 0.1 mass % and 50 mass %.
In above-mentioned adhesive composition, the weight average molecular weight of above-mentioned triblock polymer (a) is preferably 60, and more than 000
And less than 400,000.
In above-mentioned adhesive composition, by the total amount of above-mentioned triblock copolymer (a) Yu above-mentioned triblock copolymer (b)
When being set to 100 mass parts, the use level of above-mentioned tackifying resin (c) is preferably below more than 15 mass parts and 40 mass parts.
In above-mentioned adhesive composition, the composition monomer of the segment B of above-mentioned triblock copolymer (b) 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) is own with acrylic acid-2-ethyl
The match ratio of ester (2EHA) is preferably BA: 2EHA=75: 25～5: 95 by quality ratio.
Above-mentioned adhesive composition can possibly together with above-mentioned triblock copolymer (a) and above-mentioned triblock copolymer (b)
There is the softening agent (d) of the compatibility.
Now, above-mentioned softening agent (d) is preferably selected from having the segments A with above-mentioned triblock copolymer (a) and segment B is same
One kind or two or more compound in AB type diblock copolymer, acrylic compounds oligomer and the aqueous rubber of the segment of sample.
It addition, above-mentioned tackifying resin (c) is preferably rosin series resin.
It 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, be there is by use polymer based on the acrylic acid series triblock copolymer of regulation structure,
And use containing the adhesive composition making to contain in this base polymer the polymeric blends of regulation tackifying resin, thus
The adhesive tape that stationarity is excellent can be obtained.
Detailed description of the invention
Hereinafter, the embodiment being suitable for the present invention is described in detail.
It is explained, according to following order, the adhesive composition of the present invention is illustrated.
The composition of 1 adhesive composition
1-1 triblock copolymer (a)
1-2 triblock copolymer (b)
1-3 tackifying resin (c)
Any composition of 1-4
The form of 2 adhesive compositions
The purposes of 3 adhesive compositions
The composition of adhesive composition
The adhesive composition of the present invention be containing polymer based on 2 kinds of ABA type triblock copolymer (a) and (b),
But also at least contain the compositions of tackifying resin (c), except bonding force, viscosity, retentivity characteristic in addition to, above-mentioned stationarity is also
Excellent.Hereinafter, successively each composition in the adhesive composition of the present invention is illustrated.
<triblock copolymer (a)>
Triblock copolymer (a) is to comprise the segments A based on methacrylate and based on acrylate
The ABA type triblock copolymer of segment B.Here, " segment " described in the present invention refers to constitute respectively in triblock copolymer
The construction unit of block, such as, at construction unit (polymer or the oligomer) A comprising monomer a, the structure list that comprises monomer b
The ABA type that unit (polymer or oligomer) B and construction unit (polymer or the oligomer) A comprising monomer a is combined into successively
In the case of triblock copolymer, construction unit A, B respectively become segments A, B (in triblock copolymer (b) described later also together
Sample).
(segments A)
As the segments A of triblock copolymer (a), as long as using methacrylate as the chain of the main body being constituted monomer
Section, then be not particularly limited, as this kind of 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 cyclohexyl, methacrylic acid 2-methyl cyclohexyl,
Methacrylic acid 3-methyl cyclohexyl, methacrylic acid 4-methyl cyclohexyl, methacrylic acid 2-phenoxy ethyl, metering system
Acid 2-methoxy acrylate, methacrylic acid 2-(N, N-dimethylamino) ethyl ester, methacrylic acid trifluoro methyl ester, methacrylic acid are just
The most own ester of pentyl ester, methacrylic acid, 2-Ethylhexyl Methacrylate, lauryl methacrylate, methacrylic acid ten
Trialkyl ester, stearyl methacrylate, methacrylic acid 2-methoxyl group pentyl ester, methacrylic acid 2-(N, N-dimethylamino) penta
Ester, methacrylic acid perfluor pentyl ester, methacrylic acid 2-trimethoxysilyl pentyl ester etc..
In above-mentioned monomer, in order to improve the adhesion characteristic (especially at the retentivity of high temperature) of bonding adjuvant, as
Segments A constitute monomer main body, be preferably used methyl methacrylate, ethyl methacrylate, n propyl methacrylate,
The monomers such as the ester that the alcohol of the methacrylic acids such as isopropyl methacrylate and carbon number less than 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, containing more than 50%, more preferably contains more than 80%, further preferably containing more than 90%.
It addition, for the composition monomer of the segments A of triblock copolymer (a), as except above-mentioned methacrylate
The monomer that can use in addition, can enumerate such as: Methacrylamide, N-methyl methacrylamide, N-ethyl-methyl third
The first such as acrylamide, N-isopropyl acrylamide, N, N-dimethylmethacryl amide, N, N-diethyhnethacrylamide
Base acrylic amide；Acrylamide, N methacrylamide, N-ethyl acrylamide, NIPA, N, N-diformazan
Base acrylamide, N, the acrylic amide such as N-acrylamide；Methacrylic acid, acrylic acid .beta.-methylacrylic acid, maleic acid, horse
Come anhydride, fumaric acid etc. and there is the ethylene base system monomer of carboxyl；The fragrance such as styrene, α-methyl styrene, p-methylstyrene
Race's ethylene base system monomer；Butadiene, isoprene equiconjugate diene monomer；The alkene such as ethylene, propylene；6-caprolactone, in penta
Lactones such as ester etc..
(segment B)
Then, as the segment B of triblock copolymer (a), as long as using acrylate as the main body being constituted monomer
Segment, then be not particularly limited, and as this kind of acrylate, just can enumerate such as acrylic acid methyl ester., ethyl acrylate, acrylic acid
Propyl ester, isopropyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid
The most own ester, 2-EHA, lauryl ester, acrylic acid tridecane ester, stearyl acrylate ester, acrylate
Ester, isobornyl acrylate, acrylic acid 2-methoxy acrylate, acrylic acid 2-(N, N-dimethylamino) ethyl ester, acrylic acid trifluoro
Methyl ester, acrylic acid trimethoxysilyl propyl ester, lauryl acrylate, acrylic acid 2-methylbutyl butenoate, acrylic acid 4-methyl-2-
Pentyl ester, n-octyl, Isooctyl acrylate monomer, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester etc..
It addition, for the composition monomer of the segment B of triblock copolymer (a), as in addition to above-mentioned acrylate
The monomer that can use, can enumerate such as: 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 constitute monomer methyl acrylic ester)；Methacrylamide, N-methyl first
Base acrylamide, N-ethyl methacrylamide, N-isopropyl acrylamide, N, N-dimethylmethacryl amide, N,
The methacryl amines such as N-diethyhnethacrylamide；Acrylamide, N methacrylamide, N-ethyl acrylamide,
NIPA, N,N-DMAA, N, the acrylic amide such as N-acrylamide；Metering system
Acid, acrylic acid .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid etc. have the ethylene base system monomer of carboxyl；Styrene, adjacent methyl
The aromatic vinyl base system monomer such as styrene, p-methylstyrene；Butadiene, isoprene equiconjugate diene monomer；Ethylene,
The alkene such as propylene；Lactone such as 6-caprolactone, valerolactone etc..
(weight average molecular weight)
The adhesive composition of the present invention has the stationarity of excellence, and this stationarity is by the weight of triblock copolymer (a)
The impact 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, the most not only bonding force of adhesive composition, cohesion
The general characteristic such as power, viscosity reduces, and stationarity also reduces, the most preferred.In order to improve above-mentioned characteristic further, three
The weight average molecular weight of block copolymer (a) is more preferably 110, and more than 000, more preferably 130, more than 000, particularly preferably
It is more than 150,000.On the other hand, it is suitable for the mobility of melt-shaping owing to needing to have, therefore triblock copolymer (a)
Weight average molecular weight be preferably less than 400,000.In order to improve above-mentioned effect further, the weight average of triblock copolymer (a)
Molecular weight is more preferably less than 300,000.
It is explained, as the weight average molecular weight in the present invention, uses poly-by utilize gel permeation chromatography (GPC) to 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
It is 5～30 mass %, more preferably 5～25 mass %, particularly preferably 10～20 mass %.
(preparation method)
As the triblock copolymer (a) of the present invention, can synthesize by making starting monomer, it is possible to use city
The product sold.As polymerization, there is no particular restriction, such as, anionic polymerization, atom freedom of movement base can be used poly-
Legal (ATRP) etc..The detailed description to each polymerization is omitted, as anionic polymerization, it is possible to use such as with organic at this
Alkali metal compound carry out in the presence of the inorganic acid salts such as the salt of alkali metal or alkaline-earth metal as polymerization initiator cloudy from
The method of son polymerization, carry out in the presence of organo-aluminum compound using organic alkali metal compound as polymerization initiator cloudy from
The method of son polymerization, the method etc. carrying out anionic polymerisation using organic RE metalloid complex as polymerization initiator are known
Method, as ATRP, it is possible to use such as golden in transition as initiator using organohalogen compounds or sulfonyl halide based compound
Belong to known methods such as carrying out the method be polymerized in the presence of compound, nitrogen-containing compound.As commercially available product, can enumerate and such as may be used
" CLARITY (registered trade mark) series " that happy beautiful (strain) makes etc..
<triblock copolymer (b)>
Triblock copolymer (b) and triblock copolymer (a) are similarly the segments A comprised based on methacrylate
ABA type triblock copolymer with the segment B based on acrylate.But, there is acrylic acid-2-ethyl caproite conduct
The aspect constituting monomer of segment B, triblock copolymer (b) has the structure different from triblock copolymer (a).
The also cooperation in addition to above-mentioned triblock copolymer (a) of the adhesive composition of the present invention has Tg fourth more positive than acrylic acid
The lower acrylic acid-2-ethyl caproite of ester is as the copolymer (b) constituting monomer of the segment B in ABA type three block, thus removes
Stationarity can also be significantly improved outside these characteristics generally required to binding agent of bonding force, viscosity, retentivity.Enable in particular to show
Write improve as from coordinate the effect brought of triblock copolymer (b), be fixed as at general's attaching thing stationeries such as () such as ground paper
During tubular isotactic shaped produce be such as resistant to want to return to original form repulsive force (attach thing do not shell
From) characteristic (repulsion stationarity).Hereinafter, triblock copolymer (b) is described in detail.
(segments A)
The segments A of triblock copolymer (b), as the segments A of above-mentioned triblock copolymer (a), is therefore omitted at this
Detailed description thereof.Being explained, in the adhesive composition of the present invention, the segments A of triblock copolymer (a) is embedding with three
The segments A of section copolymer (b) can be identical segment, it is also possible to for different segments, but, if consideration triblock copolymer
A the compatibility of () and triblock copolymer (b), the segments A the most preferably making both is identical.
(segment B)
The segment B of triblock copolymer (b) needs have acrylic acid-2-ethyl caproite as constituting monomer as mentioned above,
Can also have " other composition monomer ".As " other composition monomer " now, it is possible to use can be as three blocks
The segment B of copolymer (a) constitutes the monomer that monomer uses.Wherein, from going out in terms of the compatibility of triblock copolymer (a)
Send out, as " other composition monomer ", n-butyl acrylate is preferably used.That is, the composition of the segment B of triblock copolymer (b)
Monomer is preferably n-butyl acrylate and acrylic acid-2-ethyl caproite.
Alternatively, it is also possible to use n-butyl acrylate as the composition monomer of 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 this scope, so that fixed raising effect of adhesive composition uprises.
In order to improve fixed raising effect further, the match ratio preferably making 2EHA is higher, specifically, and more preferably BA:
2EHA=75: 25～5: 95, more preferably 60: 40～5: 95.
It is explained, " other compositions in the adhesive composition of the present invention, in the segment B of triblock copolymer (b)
Monomer " can be identical with the composition monomer of the segment B of triblock copolymer (a), it is also possible to different, but, if considering three blocks
Copolymer (a) and the compatibility of triblock copolymer (b), the composition monomer the most preferably making both is identical.
(weight average molecular weight)
From practicality, from the viewpoint of stably manufacture, the triblock copolymer (b) in the adhesive composition of the present invention
The preferred scope of weight average molecular weight 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, has problems in practical, if weight average molecular weight is more than 200,000, then viscosity is too high, therefore on manufacturing
Existing problems.
It is explained, as the weight average molecular weight in the present invention, uses poly-by utilize gel permeation chromatography (GPC) to 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
It is 10～40 mass %, more preferably 15～30 mass %, particularly preferably 20～25 mass %.
(preparation method)
As the triblock copolymer (b) of the present invention, can synthesize by making starting monomer, it is possible to use city
The product sold.As polymerization, there is no particular restriction, and the concrete example of polymerization is as triblock copolymer (a).As city
Sell product, " CLARITY (registered trade mark) series " that such as Kuraray (strain) makes etc. can be enumerated.
(triblock copolymer (a) and the match ratio of triblock copolymer (b))
In the adhesive composition of the present invention, in order to effectively embody stationarity, need 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)
The match ratio of total amount) be more than 0.1 mass %.Thus, the fixed raising effect making adhesive composition significantly uprises.
On the other hand, if the match ratio of triblock copolymer (b) is too high, then based on polymer performance reduce, the most not only glue
Make a concerted effort, the general characteristic such as viscosity, retentivity 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 making the match ratio of triblock copolymer (b) is below 50 mass %.
In order to improve fixed raising effect further, the lower limit of the use level of triblock copolymer (b) be preferably 1 mass % with
On, more than more preferably 3 mass %, more preferably more than 5 mass %, more than particularly preferably 10 mass %.The opposing party
Face, in order to improve fixed raising effect further and suppress the reduction of general characteristic, joining of triblock copolymer (b)
The higher limit of resultant is preferably below 40 mass %, below more preferably 30 mass %, below particularly preferably 20 mass %.
<tackifying resin (c)>
The adhesive composition of the present invention must become possibly together with tackifying resin (c) conduct except above-mentioned base polymer beyond the region of objective existence
Point.Only can be had as general adhesive composition by above-mentioned triblock copolymer (a) and triblock copolymer (b)
Function, but bonding force is low, and impracticable.Therefore, the adhesive composition of the present invention by containing tackifying resin (c), from
And bonding force is improved to sufficient level in practical, and meet bonding force, viscosity, retentivity these as binding agent
General characteristic.
(with the compatibility of triblock copolymer)
Here, tackifying resin (c) is to have the compatibility with triblock copolymer (a) and triblock copolymer (b) so that energy
Enough with triblock copolymer (a) and the resin of triblock copolymer (b) formation polymeric blends.As this kind, there is the compatibility
Resin, there is no particular restriction, it is possible to use such as rosin series, terpenic series etc..As rosin series resin, such as Colophonium can be enumerated
Ester, hydrogenated wood rosin glycerol ester, non-homogenizing rosin ester, newtrex ester, gum rosin (gum rosin), Starex, maleic rosin
(Maleated rosin), maleic acid modified Colophonium etc., as terpenic series resin, can enumerate such as terpene phenolic resin, hydrogenation
Terpene phenolic resin, aromatic modified terpene resin, aromatic modified hydrogenated terpene resin hydrogenated terpene resin, with australene,
The terpenic series resin that nopinene, limonene etc. are main body.Wherein, from the viewpoint of improving stationarity, as the increasing of the present invention
Viscosity resin, is preferably used rosin series resin.
(softening point)
It addition, as the tackifying resin (c) of the present invention, the tackifying resin using at least one softening point to be more than 100 DEG C.
By coordinating the tackifying resin (c) that this kind of softening point is high, thus except bonding force, viscosity, these institutes usual to binding agent of retentivity
Stationarity can also be significantly improved outside the characteristic required.Especially, by coordinating (more than 100 DEG C) tackifying resin that softening point is high
(c) such that it is able to significantly improve will attach thing stationeries such as () such as picture posters be attached at regulation by attaching face (such as wall
Face) time produce be such as resistant to by attaching the lax of thing or stress that warpage produces, the vertical direction that produced by gravity
(attaching thing not peel off from by attaching face) characteristic (shearing stationarity) of shearing force.Go out from the viewpoint improving this characteristic further
Sending out, 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, then resin becomes really up to the mark, it is impossible to obtain being suitable as gluing
The viscosity of mixture.Therefore, the softening point of tackifying resin (c) be preferably less than 200 DEG C, more preferably less than 170 DEG C, the most excellent
Elect less than 165 DEG C, most preferably less than 160 DEG C as.Additionally, it is preferred that to have the tackifying resin of above-mentioned preferred softening point
Want composition (using the gross mass of whole tackifying resins as benchmark, be more than 50 mass %).
(use level)
When the total amount of triblock copolymer (a) Yu above-mentioned triblock copolymer (b) is set to 100 mass parts, thickening tree
The use level of fat (c) is preferably below more than 15 mass parts and 40 mass parts.If the use level of tackifying resin (c) is less than 15 mass
Part, then there is the risk that its additive effect (bonding force or fixed raising effect) becomes insufficient.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) is more than 40 mass parts, then there is the risk that viscosity reduces.
<any composition: softening agent (d)>
The adhesive composition of the present invention can be possibly together with softening agent (d) as arbitrarily becoming except above-mentioned base polymer beyond the region of objective existence
Point.Only can have the binding agent as the present invention by above-mentioned triblock copolymer (a) and triblock copolymer (b) to combine
The function of thing, but bonding force is low, and the most insufficient.Therefore, the adhesive composition of the present invention is by containing
Have a softening agent (d), thus bonding force improved to practical sufficient level, and meet bonding force, viscosity, retentivity these
General characteristic as binding agent.
(with the compatibility of triblock copolymer)
Here, softening agent (d) be with triblock copolymer (a) and triblock copolymer (b), there is the compatibility so as to
With the resin that triblock copolymer (a) and triblock copolymer (b) form polymeric blends.As this kind, there is the compatibility
Compound, there is no particular restriction, the segment as can enumerating the segments A such as having with triblock copolymer (a) and segment B
AB type diblock copolymer, acrylic polymer, acrylic compounds oligomer, aqueous rubber (such as polybutene, polyisobutylene,
Polyisoprene), technical oil, phthalate, adipic acid esters, sebacic acid ester, aliphatic ester, polyethers etc..
These compounds can be used alone one, it is also possible to is applied in combination two or more.In these compounds, from three blocks altogether
Polymers (a) and the good aspect of triblock copolymer (b) compatibility are set out, be particularly preferably used alone diblock copolymer or
It is applied in combination diblock copolymer and acrylic compounds oligomer.
As above-mentioned diblock copolymer, as long as there is the segments A of above-mentioned triblock copolymer (a) and segment B is same
Segment, then be not particularly limited.But, if considering softening agent (d) and triblock copolymer (a) and triblock copolymer (b)
The compatibility, the most preferably make the segments A of diblock copolymer and B comprise the segments A with triblock copolymer (a) and B phase respectively
Same composition monomer.Now, in order to make the compatibility the highest, it is preferred that the composition monomer of the segments A of triblock copolymer (b)
Identical with the segments A of diblock copolymer and triblock copolymer, above-mentioned " other compositions of the segment B of triblock copolymer (b)
Monomer " identical with the segment B of diblock copolymer and triblock copolymer.It addition, in order to make and triblock copolymer (a) and three
The compatibility of block copolymer (b) uprises, and preferably aforesaid propylene acid based oligomerization thing, aqueous rubber.
(use level)
From the viewpoint of the viscosity improving adhesive composition, softening agent (d) can be coordinated.By triblock copolymer
When the total amount of () and above-mentioned triblock copolymer (b) is set to 100 mass parts a, the use level of softening agent (d) is preferably 250 mass
Below Fen.If the use level of softening agent (d) is more than 250 mass parts, then exists and cause the retentivity of adhesive composition to reduce
Probability.Therefore, in order to improve stationarity, below more preferably 200 mass parts, more preferably below 150 mass parts.Separately
Outward, lower limit is not particularly limited, for example, 50 mass parts.
<any composition: other>
It addition, in the adhesive composition of the present invention can not hinder add in the range of effect of the present invention a kind of or
Two or more filler, antioxidant, heat stabilizer, UV absorbent, light stabilizer, antistatic additive, fire retardant, foaming
Other additives such as agent, coloring agent, stain.
" form of adhesive composition "
Above, the composition of the adhesive composition of the present invention is explained, but, this adhesive composition
Can also be for make above-mentioned triblock copolymer (a), triblock copolymer (b), tackifying resin (c), softening agent (d) and arbitrarily to become
(binder materials) is divided to be dissolved in the solvent-based adhesive compositions of regulation solvent, it is also possible to for making above-mentioned binder materials
Melted and mixing hot-melt adhesive composition.It is explained, as the solvent used in the case of solution-type,
The such as organic solvent such as toluene, ethyl acetate can be used.
" purposes of adhesive composition "
The adhesive composition of present invention mentioned above may be used for the purposes such as adhesive tape (one or two sides).Hereinafter,
As the example of purposes of the adhesive composition of the present invention, the adhesive composition that the two sided coatings at base material is above-mentioned is formed
Double-sided adhesive tape illustrate.It is explained, in the case of single-sided adhesive tape, except the single spreading binding agent at base material
In addition, also it is same.
The double-sided adhesive tape of the adhesive composition of the application present invention combines at the binding agent that the two sided coatings of base material is above-mentioned
Thing, and adhere to peeling paper as required on the surface of adhesive composition.
As base material, as long as can the shape such as membranaceous, lamellar of coating adhesive compositions, then there is no particular restriction,
Can use such as: the paper such as kraft paper, Japan paper, crepe paper (crepe)；Comprise artificial silk, cotton, acetas, polyethylene (PE), gather
The non-woven fabrics of propylene (PP) etc.；Cellophane (cellophane), vinyl chloride, PE, oriented polypropylene (OPP), poly terephthalic acid
The resin moldings such as glycol ester (PET), tetrafluoroethene, polyimides, Merlon (PC), polystyrene (PS)；Polyurethane, PE,
The foamed resins such as butyl rubber；The metal forming such as aluminum, copper；The sheet rubbers etc. such as natural rubber, SBR, butyl rubber.
It addition, as the method for coating adhesive compositions on base material, be also not particularly limited, it is possible to use make bonding
Method (molten exhibition method) that agent material dissolution is coated after organic solvent again, multiple hot-rolling is utilized to make after it is thinning (thin go out)
The method (rolling process) that is coated again, make binder materials heat fusing after the method (hot melt) that is coated again etc. known
Method.
Embodiment
Below, utilize embodiment and comparative example that the present invention is further illustrated, but the present invention is not by these
Any restriction of example.
<raw-material explanation>
Use following raw material, make embodiment 1～27, the double-sided adhesive tape of comparative example 1～7.
[triblock copolymer (a)]
Triblock copolymer (a-1): methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three blocks
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents is 16 mass %), molecular weight be 140,
000
Triblock copolymer (a-2): methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three blocks
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents is 22 mass %), molecular weight be 115,
000
Triblock copolymer (a-3): methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three blocks
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents is 23 mass %), molecular weight be 75,
000
Triblock copolymer (a-4): methyl methacrylate (MMA)-n-butyl acrylate (n-BA) copolymer (three blocks
Body, hard segment (segments A) are MMA, soft chain segment (segment B) is n-BA, hard segment contents is 12 mass %), molecular weight be 180,
000
[triblock copolymer (b)]
Triblock copolymer (b-1): methyl methacrylate-n-butyl acrylate-2-EHA (2EHA)
(three block bodies, hard segment be MMA to copolymer, soft chain segment is n-BA and 2EHA, n-BA: 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 bodies, hard segment be MMA to copolymer, soft chain segment is n-BA and 2EHA, n-BA: 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 bodies, hard segment be MMA to copolymer, soft chain segment is n-BA and 2EHA, n-BA: 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 blocks
Body, hard segment are MMA, soft chain segment is 2EHA, hard segment contents is 23 mass %) molecular weight is 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)]
(diblock body, hard segment are CLARITY LA1114: methyl methacrylate-n-butyl acrylate copolymers
MMA, soft chain segment are n-BA)
ARUFON (registered trade mark) UP-1000: without the acrylic polymer of functional group's type
<manufacture method>
Utilize molten exhibition legal system to make two sides according to the use level (unit is mass parts) shown in table 1 below above-mentioned raw material to glue
Crossed belt.Specifically, adding above-mentioned raw material with the use level shown in table 1 below in toluene, stirring makes this raw material dissolve,
It is fabricated to solvent-based adhesive compositions (solid component concentration is 50 mass %).Then, by the adhesive composition profit of gained
It is coated on peeling paper with applicator.After the baking oven of 100 DEG C is dried 3 minutes, non-woven fabrics (I) is pasted with adhesive composition
Close.Then, on peeling paper, apply adhesive composition as described above, after drying, fit with the non-woven fabrics side of (I), system
Make double-sided adhesive tape.The coating weight on the two sides of adhesive composition is all set to 25g/m2.Finally, in order to make binding agent and non-woven fabrics
Grappling (anchoring) good, and implement the heat lamination of 120 DEG C, make embodiment 1～27 and the two sides of comparative example 1～7 glue
Crossed belt.
<evaluation methodology>
For the embodiment 1 made in the manner described above～27 and the double-sided adhesive tape of comparative example 1～7, utilize following
Method carries out the evaluation of each characteristic.
(1) fundamental characteristics (SUS bonding force, probe tack, ball viscosity, glass retentivity)
About fundamental characteristics, it is determined according to JIS Z 0237.But, in the evaluation of SUS bonding force, as examination
Test plate and compression bonding method, use the method different from the method for regulation in JIS Z 0237.Specifically, at SUS bonding force
In evaluation, as bread board, re-use after in JIS G 4305, the SUS304 steel plate of regulation completes surface grinding.It addition,
During crimping, make the roller of 2000g with reciprocal 1 time of the speed of 300mm/ minute, place 20～40 minutes after crimping, afterwards, determine
Bonding force (other are as JIS Z 0237).
(2) stationarity test is sheared
At A2 size, weight per unit area 87g/m2, thickness 125 μm ASKUL color coating paper (picture poster) corner patch
The double-sided adhesive tape that attached 15mm is square.Afterwards, with finger, color coating paper strength is pressed and attaches to be pasted with SANGETSU chlorine
On the wall of ethylene wallpaper SP7204, place more than 12 hours in the environment of 40 DEG C, about 10%RH.Now, picture poster is measured
From attach after to from wall fall fall time, evaluated according to following benchmark.
A: fall time is more than 4 days
B: fall time is more than 24 hours and less than 4 days
C: fall time is more than 5 hours and less than 24 hours
D: fall time was less than 5 hours
(3) stationarity test is repelled
With A4 size, weight per unit area 500g/m2One end pair of minor face of modern village's paper work making sheet mesh table paper (ground paper)
Attaching the wide double-sided adhesive tape of 15mm together, ground paper rolled by the paper tube along diameter 78mm, fits with the minor face of the other end, makes
Cylinder.Now, the splitting time opened after attaching (fitting part of ground paper is peeled off) is measured to cylinder, according to following
Benchmark is evaluated.
A: splitting time is more than 6 days
B: splitting time is more than 24 hours and less than 6 days
C: splitting time is more than 5 hours and less than 24 hours
D: splitting time was less than 5 hours
<evaluation result>
Understand: by being also added with PMMA/Pn-BA-2EHA/PMMA except PMMA/Pn-BA/PMMA triblock copolymer beyond the region of objective existence, from
And when maintaining bonding force, viscosity and make such as to be fixed as by ground paper that the paper work of tubular is such is capable of withstanding when retentivity
The repulsion stationarity of the repulsive force peeled off significantly improves.Being explained, about fundamental characteristics, in embodiment 1, SUS bonds
Power is 7.6 [N/15mm], and probe tack is 9.3 [N/5mm φ], and ball viscosity is No.12, and glass retentivity is 0.2 [mm/15
20·1kg·1h].It addition, in other embodiment and comparative example, obtain the result the most equal with embodiment 1.
It addition, understand: the tackifying resin high by adding softening point, thus also make such as to paste a surname in addition to repelling stationarity
Pass picture such be resistant to be produced by the lax of paper or warpage stress, the cutting of the shearing force of vertical direction that produced by gravity
Cut stationarity to improve.
[table 1]
[table 1]
[table 2]
[table 2]
[table 3]
[table 3]
Above, the preferred embodiment of the present invention is illustrated, but the present invention is not limited by above-mentioned embodiment
Fixed.I.e., it is possible to be interpreted as those skilled in the art in the range of the invention that claims are recorded it is conceivable that other are real
Execute mode or various variation falls within the technical scope of the present invention.
Claims (8)
1. an adhesive composition, it contains:
Comprise the segments A based on methacrylate and the ABA type triblock copolymer of the segment B based on acrylate
Thing (a),
Comprise the segments A based on methacrylate and the ABA type triblock copolymer of the segment B based on acrylate
Thing (b) and
The softening point with described triblock copolymer (a) and described triblock copolymer (b) with the compatibility is more than 110 DEG C
Tackifying resin (c),
There is the acrylic acid-2-ethyl caproite composition monomer as the segment B of described triblock copolymer (b),
Described triblock copolymer (b) is relative to the total amount of described triblock copolymer (a) and described triblock copolymer (b)
Match ratio is below more than 0.1 mass % and 50 mass %.
Adhesive composition the most according to claim 1, wherein, the weight average molecular weight of described triblock polymer (a) is
More than 60,000 and less than 400,000.
3. according to the adhesive composition according to any one of claims 1 to 3, wherein, by described triblock copolymer (a) with
When the total amount of described triblock copolymer (b) is set to 100 mass parts, the use level of described tackifying resin (c) be 15 mass parts with
Go up and below 40 mass parts.
4. according to the adhesive composition according to any one of claims 1 to 3, wherein, the chain of described triblock copolymer (b)
The composition monomer of section B is n-butyl acrylate and acrylic acid-2-ethyl caproite.
Adhesive composition the most according to claim 4, wherein, the propylene in the segment B of described triblock copolymer (b)
Acid N-butyl, i.e. BA are BA: 2EHA=75: 25～5 with the match ratio of acrylic acid-2-ethyl caproite, i.e. 2EHA by quality ratio:
95。
6. according to the adhesive composition according to any one of Claims 1 to 5, its possibly together with described triblock copolymer
A () and described triblock copolymer (b) have the softening agent (d) of the compatibility.
Adhesive composition the most according to claim 6, wherein, described softening agent (d) is for three embedding with described selected from having
The segments A of section copolymer (a) and the same diblock copolymer of AB type of segment of segment B, acrylic compounds oligomer and aqueous
One kind or two or more compound in rubber.
8. an adhesive tape, it is coated with the binding agent combination according to any one of claim 1～7 at least one side of base material
Thing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014011037 | 2014-01-24 | ||
| JP2014-011037 | 2014-01-24 | ||
| PCT/JP2015/051627 WO2015111646A1 (en) | 2014-01-24 | 2015-01-22 | Acrylic pressure-sensitive-adhesive composition and pressure-sensitive-adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105829479A true CN105829479A (en) | 2016-08-03 |
| CN105829479B 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 |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6431854B2 (en) |
| KR (1) | KR102228806B1 (en) |
| CN (1) | CN105829479B (en) |
| WO (1) | WO2015111646A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227288A (en) * | 2018-12-27 | 2021-08-06 | 株式会社可乐丽 | Laminate having structure body including through-hole |
| CN113402685A (en) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2958582A1 (en) * | 2014-08-20 | 2016-02-25 | Kuraray Co., Ltd. | Acrylic pressure-sensitive adhesive compositions and pressure-sensitive adhesive products |
| 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 |
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| JP5051967B2 (en) | 2004-04-23 | 2012-10-17 | 株式会社クラレ | Acrylic block copolymer composition |
| 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 |
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2015
- 2015-01-22 JP JP2015559099A patent/JP6431854B2/en active Active
- 2015-01-22 CN CN201580003157.2A patent/CN105829479B/en active Active
- 2015-01-22 WO PCT/JP2015/051627 patent/WO2015111646A1/en active Application Filing
- 2015-01-22 KR KR1020167022372A patent/KR102228806B1/en active IP Right Grant
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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 |
| WO2007029783A1 (en) * | 2005-09-07 | 2007-03-15 | Kuraray Co., Ltd. | Acrylic adhesive composition and adhesive product |
| JP2011028069A (en) * | 2009-07-28 | 2011-02-10 | Kuraray Co Ltd | Method for producing adhesive optical film |
| WO2013162056A1 (en) * | 2012-04-27 | 2013-10-31 | Kuraray Co., Ltd. | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive products |
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| CN113227288A (en) * | 2018-12-27 | 2021-08-06 | 株式会社可乐丽 | Laminate having structure body including through-hole |
| CN113227288B (en) * | 2018-12-27 | 2022-08-02 | 株式会社可乐丽 | Laminate having structure body including through-hole |
| TWI812826B (en) * | 2018-12-27 | 2023-08-21 | 日商可樂麗股份有限公司 | Laminated body having a structure including through-holes |
| CN113402685A (en) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6431854B2 (en) | 2018-11-28 |
| WO2015111646A1 (en) | 2015-07-30 |
| CN105829479B (en) | 2017-12-29 |
| JPWO2015111646A1 (en) | 2017-03-23 |
| KR20160113159A (en) | 2016-09-28 |
| KR102228806B1 (en) | 2021-03-18 |
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