JP2003327944A - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an adhesive composition improved in tackiness and low temperature adhesivity, having heat-activating and heat re-peelable properties. <P>SOLUTION: This adhesive composition comprises a sticky first polymer having phenyl group and hydroxy group, a crystalline second polymer and an amorphous third polymer having -80 to 0°C glass transition point and selected from the group consisting of a polyester polyol, a polycarbonate polyol and their urethane compounds. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to an adhesive composition.
And more specifically, heat activated adhesives and heat removable adhesives
And an adhesive composition having both properties. [0002] BACKGROUND OF THE INVENTION One category of adhesive compositions is well known.
And pressure-sensitive adhesive compositions. Pressure sensitive adhesive composition
Things are also called adhesives. Adhesive has tack at room temperature
Pressure only without activation by water, solvent or heat
In general, immediately demonstrate practical adhesive strength that can withstand practical use
Can be. One example of such an adhesive is disclosed in
No. 186,265, which discloses an acid component.
Acrylic having no glass transition point of -10 ° C or less
-Based polymer 50 to 5% by mass and aliphatic polycarbonate geo
50 to 95% by mass of a polyester polymer containing
It is. On the other hand, adhesive compositions include, for example, JP-A-20
As disclosed in Japanese Patent Application No. 01-316658,
Can be joined by developing heat or tack by receiving heat from the part
There are also things. Such an adhesive composition is referred to as a heat activated adhesive.
Also called. Heat activated adhesives include US Pat. No. 5,192,
Shows removability as disclosed in specification No. 612
There is something. Such removable thermoactive adhesives are
Pressure-sensitive welding containing adhesive polymer (eg acrylic polymer)
Non-adhesive at room temperature (25 ° C) with adhesive base resin
Crystalline polymer (eg, polycaprolactone)
Detackification consisting of deadhesive resin and inorganic particles (for example, silica)
Particles. [0004] Also, some heat activated adhesives are
Shows removability, required after bonding, during use or after completion of use
Can be separated from the adherend in accordance with the condition. Such heating
An example of a removable adhesive is US Pat. No. 5,412,
No. 035, which is 20-40 ° C.
Adhesives that are effective at temperatures in the range of
Krill-based pressure-sensitive adhesives) and crystalline polymers (for example, having 1 carbon atom)
(Meth) acrylate having 4 to 22 alkyl groups
). A similar type of heat-active adhesive is disclosed in
It is also disclosed in JP-A-00-119624. This addition
Polyester as a crystalline polymer for heat-removable thermo-active adhesive
Caprolactone is used. Also, in the adhesive,
Adhesive polymers containing hydroxyl and phenyl groups
At temperatures above the melting point of the polycaprolactone
Is very compatible with polycaprolactone
You. Such a heat-activated adhesive has a crystallized polish at room temperature.
Licaprolactone shows almost no stickiness,
Very high after heating to melt polycaprolactone
High adhesive strength. [0006] SUMMARY OF THE INVENTION The above-mentioned heat-removable type
Heat-activated adhesives are often processed into films
Exterior and indoor decorative sheets and marking films (hereinafter
It is called "decorative sheet etc." ). in this case,
Decorative sheets etc. and adherends via such a heat activated adhesive
Can be joined with the highest possible tack.
It is desirable for installers such as Also, for example, decoration
Sheets, etc., can be easily applied even in cold regions.
In order to use such a heat-removable heat-activated adhesive,
To maintain relatively high adhesion at relatively low temperatures.
Is desirable. Therefore, the present invention relates to tack and low temperature.
Improved thermal adhesion and heat-removable contact with improved adhesion
It is intended to provide a dressing composition. [0007] According to the present invention, there is provided the above-mentioned object.
Is a tacky secondary having phenyl and hydroxyl groups.
One polymer, a crystalline second polymer, and -80 ° C to 0 ° C.
° C glass transition point, polyester polyol,
Recarbonate polyols and their urethane compounds
At least one non-crystalline material selected from the group consisting of
The problem is solved by an adhesive composition comprising a third polymer. [0008] BEST MODE FOR CARRYING OUT THE INVENTION
This will be described in detail. However, the present invention is limited to these embodiments.
It is easily understood by those skilled in the art that it is not specified. Of the present invention
The adhesive composition has an adhesive first polymer and crystallinity.
And a non-crystalline third polymer.
No. The first polymer is tacky at room temperature of about 25 ° C.
Or a tacky polymer showing tackiness, usually 10 to 10
95% by weight, preferably 20 to 90% by weight, more preferably
30 to 85% by mass contained in the adhesive composition,
Compatible with the second polymer at a temperature higher than the melting point of the second polymer
be able to. Typical first polymer, viscous
The polymer is acrylic polymer, acrylonitrile
Nitrile-butadiene copolymer such as tadiene rubber (NBR)
Styrene such as coalesced styrene-butadiene rubber (SBR)
Butadiene copolymer, amorphous polyurethane and silicone
Selected from corn polymers and mixtures thereof.
You. [0010] Suitable tacky polymers include hydroxyl groups.
And a phenyl group in the molecule.
The compatibility with the polymer can be effectively increased. Ma
In addition, the adhesive polymer can be used, if necessary,
Crosslinked by irradiation of waves or electron beams and / or heating
Can be In this case, the above functional group is added to the adhesive polymer.
Other than epoxy groups and / or carboxyl groups,
By further introducing a crosslinkable functional group, the crosslinking reactivity
Can be given. Alternatively, a crosslinking component is added to the adhesive composition.
And crosslink the sticky polymer through it
Is also good. The cross-linking component is bifunctional or more and the cross-linkable functional group described above
There is no particular limitation as long as it is a compound that can react with. That
Such compounds usually consist of monomers or oligomers. [0011] Such suitable tacky polymers include tacky
50% by mass or more, preferably in the entirety of the functional polymer,
60% by mass or more, more preferably 70% by mass or more
You. In addition, unless the purpose and effects of the present invention are impaired,
A droxyl group, a phenyl group and an optional crosslinkable functional group,
Other tacky polymers that do not have can also be used. The preferred tacky polymers described above are commonly used.
Usually, a plurality of monomers described below: (A) Monomer having hydroxyl group in molecule (B) Monomer having a phenyl group in the molecule (C) having a crosslinkable functional group used as desired in the molecule;
Monomer Is a copolymer derived from the mixture of Also sticky
Polymer reacts carboxyl groups etc. in the molecule,
Hydroxyl and phenyl groups added
No. The above-mentioned copolymer is prepared by a well-known and commonly used method, for example, solution polymerization.
Can be manufactured. The above, having a hydroxyl group in the molecule
Monomer having monomer (A) and phenyl group in the molecule
-The basic unit derived from (B) is
Usually 30 to 100% by mass, preferably 35 to 95% by mass,
More preferably, the content is 40 to 90% by mass. Adhesive polymer
Is contained in a relatively small proportion of the basic unit,
Compatibility with the hydrophilic polymer. 30 ~ sticky polymer
When it has 60% by mass of the above basic unit, the adhesive composition
Shows adhesiveness or tack that is advantageous for pressure bonding with an adherend. A monomer having a hydroxyl group in the molecule
The basic unit derived from (A) is generally used in the adhesive polymer.
Always 0.1% by mass or more, preferably 1% by mass or more, more preferably
Contains 2 to 25% by mass. The adhesive polymer is
When this unit is contained in a relatively small proportion, the crystalline polymer
It becomes difficult to be compatible with. On the other hand, the adhesive polymer is
Effective pressure bonding to the adherend when the ratio is relatively large
It becomes difficult to do. Monomers having a crosslinkable functional group in the molecule
The basic unit derived from (C) is included in the adhesive polymer through
0-15% by mass, preferably 0.7-10% by mass, more
Preferably the molecular weight of the tacky polymer contained from 1 to 7% by weight
Is not limited as long as the object and effects of the present invention are achieved.
However, the adhesive polymer is usually 10,000 to 1,000,000
It has a weight average molecular weight of 00. The aforementioned monomers are preferably (meth) a
Acryl monomer, an acrylic adhesive polymer
-Can be guided. Hydroxyl group in the molecule
Examples of (meth) acrylic monomers having (meth) acrylic
2-hydroxyethyl acrylate, (meth) acrylic acid 2
-Hydroxypropyl, 4-hydro (meth) acrylate
Xybutyl and 2-hydroxy-3-phenoxypropyl
Acrylate. In particular, 2-hydroxy-3
-Phenoxypropyl acrylate has hydroxy
It has both silyl and phenyl groups and is a
Effectively increase compatibility with crystalline polymers.
It is preferable in that it can be cut. In addition, a compound having a phenyl group in the molecule (meth
T) Preferred examples of acrylic monomers include phenoxyethyl
Acrylate or phenoxypropyl acrylate
I will. In each of these, the phenoxy group is replaced with a phenyl group.
Have. In addition, it has a crosslinkable functional group in the molecule (
Examples of acrylic monomers include (meth) acrylic acid.
Such as unsaturated acids and glycidyl (meth) acrylate
(Meth) acrylic monomer containing epoxy group
You. All of these have a thermocrosslinkable functional group in the molecule.
You. In addition, unsaturated materials such as acryloylbenzophenone
Having a double bond and a photocrosslinkable functional group in the molecule
D) Introduce acrylic monomer to light
Crosslinkability may be imparted. Alternatively, for adhesive polymers
Thermally crosslinkable by introducing thermal and photocrosslinkable functional groups
And photocrosslinkability. In addition to the above monomers, 4 to 10 carbon
It has an alkyl group having a prime number (however,
Groups, phenyl groups and crosslinkable functional groups. ) Acri
It is desirable that the monomer (D) be further contained.
No. Examples of such acrylic monomers are acrylic acid n
-Butyl, isobutyl acrylate, isooctyl acrylate
Includes tyl and 2-ethylhexyl acrylate. The second polymer of the present invention is generally used at room temperature.
Crystalline, having a melting point of 40-60 ° C
It is a polymer. Includes such crystalline polymers
When the adhesive composition has a high cohesive force,
Shows little tackiness or tack. Temperature above melting point
The crystalline polymer melted by heating to
It is very compatible with adhesive polymers and is used in adhesive compositions.
Works as a polymeric plasticizer. As a result, the adhesive composition
Loses concentration but increases tack and joins to adherend
Can be That is, the adhesive composition of the present invention
In essence, it is a heat activated adhesive. This adhesive composition is again
When cooled to room temperature, the crystalline polymer recrystallizes.
You. As a result, the adhesive composition loses tack but loses cohesive strength.
Increase and bond with adherends with very high adhesion
Can be. The adhesive composition also has the property of being easily removed by heating.
Easy heating from the adherend without damaging the adherend
Can be removed. Because if the adhesive composition is heated
The crystalline polymer melts and loses cohesive strength and adheres
Because it reduces the power. That is, the adhesive set of the present invention
Bonding of the product to the adherend is reversible. Compatibility of adhesive polymer and crystalline polymer
In general, a change in the transparency or haze of the adhesive composition
Can be observed visually or with a polarizing microscope.
Therefore, the heating required for thermal activation and re-peeling of the adhesive composition
The amount can be easily grasped. Especially haze is accurate by color difference meter
The quality of the adhesive composition of the present invention
Useful for reason. The adhesive composition of the present invention comprises a tacky poly
And crystalline polymers are compatible and generally relatively
Has low haze. The adhesive composition of the present invention is preferably
Has a haze of 3% or less, more preferably a haze of 2% or less.
Have. Crystalline polymers are outside the scope of the present invention.
There is no particular limitation unless otherwise specified. Examples of crystalline polymers are
Crystalline polyester (eg crystalline polycaprolactone)
And / or crystalline polycarbonate. These
Including crystalline polycarbonate and 1,9-nonanediol
Crystalline polyester has heat resistance and hydrolysis resistance etc.
Relatively excellent in weather resistance. Adhesive composition containing these
Has high cohesion even when heated or in contact with moisture
Can be provided reversibly for a long period of time. Therefore,
Ming adhesive composition has excellent environmental stability and high long-term
Reliable, heat-activated desired adhesion and heating
It may exhibit ease of re-peeling. Crystalline polycarbonate is resistant to hydrolysis
It is particularly excellent, and is not suitable for adhesive compositions used under humid conditions.
Always valid. Of such crystalline polycarbonate
Examples include crystalline polycarbonate diols. Conclusion
Crystalline polycarbonate diols include, for example, ethylene carbonate.
1,6-hexene with a carbonate compound such as carbonate
Reaction products with diol compounds such as sundiol
is there. Examples of crystalline polymers include 1,9-nonanediene.
All-containing crystalline polyester diols are included.
This is the reaction between 1,9-nonanediol and dicarboxylic acid.
It is a reaction product and has high crystallinity. If necessary,
The above-mentioned crystalline polycarbonate diol and crystalline polyester
Urethane conversion of terdiol with diisocyanate
Controls the molecular weight by forming urethane compounds
Or increase compatibility with tacky polymers.
Can be. Changing the amount of the crystalline polymer to be added
Controls the tack of the adhesive composition at room temperature
can do. For example, this adhesive composition has 30
If it contains more than% crystalline polymer, tack at room temperature
Can be relatively low for effective alignment
become. The adhesive composition has a crystallinity of 20% by mass or less.
Have a relatively low Tg (below about -15 ° C)
Acrylic adhesive polymer (for example, 2-ethylhexyl)
Mainly composed of sil acrylate and / or butyl acrylate
At room temperature
Pressure-sensitive adhesives with high tackiness and easy heating and re-peeling
A product is obtained. The adhesive composition of the present invention comprises a third polymer
In addition. The third polymer has a temperature of -80 ° C to 0 ° C.
Amorphous polyester polyol with lath transition point
And / or polycarbonate polyol
You. These are the first polymer and the second polymer as polymer plasticizers.
By facilitating the compatibility of the polymer, the adhesive composition
Adhesion or tack at room temperature can be increased.
The third polymer is, preferably, like the second polymer.
Reacting the polyol portion of the
Thus, it can be converted to urethane. This allows
Compatibility effect can be enhanced or molecular weight control is advantageous
Can be done. In addition, the presence of the third polymer
Even at a relatively low temperature of about −5 ° C., this adhesive composition
A relatively high adhesive strength can be maintained. Poly above
Of ester polyols and polycarbonate polyols
Each example is preferably a polycaprolactonediol
Reaction between di- or alkanediol and dicarboxylic acid
Alkanediol and ethylene carbonate
A reaction product with such a carbonate compound. these
Has excellent compatibility with adhesive polymers and crystalline polymers
I have. The adhesive composition of the present invention is described below, for example.
Effectively processing into tape or sheet by sliding method
Can be used. However, the present invention is limited to this method.
It is not specified, and a method well-known and commonly used by those skilled in the art may be used.
No. First, a first polymer, a second polymer and a third polymer
In a solvent at a specified mixing ratio and mix
Prepare a product precursor. For mixing, use a homomixer or plastic
A device such as a netari mixer can be used. In addition,
Agents include, for example, ethyl acetate, toluene, methyl ethyl ketone.
Tons, acetone or mixtures of these
Wear. Further, the above-mentioned crosslinking agent may be added as necessary.
Can be. Next, this adhesive composition precursor was used as a base material.
Apply a predetermined amount. For coating, knife coater, roll coater
Using means such as taper, die coater or bar coater
be able to. The substrate is generally metal, paper or plastic.
It is a film consisting of a film. Such a film
The substrate is usually 5-500 μm, preferably 10-300 μm
Having a thickness of In addition, the film-shaped base material is
Transparent or reflective or retroreflective to ultraviolet light
May have, or be colored or decorated by printing etc.
May be used to form decorative sheets or marking films.
No. Next, the adhesive composition precursor was used together with the above base material.
Put in the oven. Therefore, the adhesive composition precursor
Heat and dry at a temperature and for a predetermined time to remove the solvent, and
Adhesive composition in the form of a tape or sheet having a thickness
Below, it is called "film adhesive". ). This film
The adhesive is applied to the adherend by removing the substrate or together with the substrate.
Adhere. If necessary, apply the film adhesive
May be covered and protected. Generally the liner is paper or
Made of plastic. For paper substrates that are peeled,
Usually provided with a release layer of polyethylene or silicone
I have. In the case of a release layer of silicone,
-Undercoats such as coats and polyethylene coats
Intervenes between the substrate and the release layer. Also, a desirable plastic
Stick base materials are polyethylene
Phthalate (PET). In addition, the plastic
In the case of sticks, it is desirable that
Good. A state in which fine irregularities are provided on the surface of the liner
Then, the liner and the film adhesive may be adhered to each other.
In this case, the shape corresponding to the above unevenness is transferred to the
Formed on the film adhesive surface. The irregularities are regular or
They may be arranged in an irregular pattern. In addition,
As long as the purpose and effect of the light are not impaired,
Place glass beads and use film adhesive for the above transfer
Can be scattered. The film adhesive is brought into close contact with the adherend. This
Film adhesive adheres in this state due to its tack
Excellent adhesion to the body. Then this film adhesive
Is below the melting point of the crystalline polymer (ie, the second polymer)
Heat activated film by heating to above temperature
The adhesive is adhered to the adherend. At this time, the flow of the present invention
Film adhesives have a high tack and very little
Adhesive strength that can withstand practical use by simply applying pressure to the adherend
Demonstrate. Therefore, the application of film adhesive is very
It is easy. The adherend to which the film adhesive was bonded was changed to -5
Use in a place with a relatively low temperature of about ℃ (cold area).
Can also be. The film adhesive of the present invention can be used at such low temperatures.
This is because a relatively high adhesive strength can be maintained. As needed
The film adhesive is then heated to a temperature below the melting point of the crystalline polymer.
Separation from adherend by heating to above temperature
Can be. The surface of the adherend is, for example, aluminum,
Metals such as stainless steel, copper or zinc steel sheet, polyimide,
Acrylic resin, polyurethane, melamine resin, epoxy
Organic material such as resin or vinyl chloride, or ceramic
Alternatively, it may be an inorganic oxide material such as glass. As long as the objects and effects of the present invention are not impaired,
A tackifier may be used in combination with a tacky polymer. Also,
Compatible with the crystalline polymer, for example, acrylic
Polymers can also be added. Such acrylic
The system polymer is, for example, the following mixture or mixed monomer
ー ： (I) 2-ethylhexyl acrylate, butyl acrylic
Alkylacrylate consisting of methyl acrylate and methyl acrylate
Rate mixture, or (Ii) not containing acrylic acid and / or methacrylic acid
It is a polymer of a mixed monomer. This acrylic polymer
Can be a non-tacky polymer. At that time, the contact of the present invention
The adhesive composition reacts with the carboxyl group of the methacrylic acid
It is desirable to include a crosslinking component. The adhesive composition of the present invention further comprises the above-mentioned adhesive composition.
Various additives other than the tackifier and acrylic polymer
May be included. Such additives include, for example,
Imparting agents, viscosity modifiers, defoamers, leveling agents, UV absorbers
Collector, antioxidant, pigment, fungicide, adhesive polymer
Elastic microspheres or non-adhesive rubber polymer
It is a catalyst that promotes the bridge reaction. BEST MODE FOR CARRYING OUT THE INVENTION
However, the present invention is not limited to these. [0035] The present invention will be specifically described below with reference to examples.
You. However, the present invention is not limited to these examples.
Needless to say.Examples 1 to 5 and Comparative Examples 1 and 2 1. Production of film adhesive Mixed solvent of ethyl acetate and toluene (ethyl acetate: toluene
Ene = 50: 50 (mass ratio)).
2 polymer, 3rd polymer (In the comparative example, the 3rd polymer is
Not used) and a cross-linking agent are mixed at the mass ratio shown in Table 1.
Then, an adhesive composition precursor was prepared. Next, this bonding
Polyurethane composition having a thickness of 35 μm
A predetermined amount was applied to the film. Then, the adhesive composition
Product precursor in oven with the above polyurethane film
I put it. Among them, the adhesive composition precursor is heated at 100 ° C.
Heat and dry for 5 minutes, mixed solvent of ethyl acetate and toluene
And then remove the polyurethane film and remove
A film adhesive having a thickness of m was made. Hereinafter, the components used for preparing the film adhesive were used.
List the minutes:First polymer (1) PSA-1: phenoxyethyl acrylate / 2-h
Droxy-3-phenoxypropyl acrylate / buty
Acrylate / acrylic acid (mass ratio 30: 15: 5
0: 5) Copolymer. (2) PSA-2: phenoxyethyl acrylate / 2-h
Droxy-3-phenoxypropyl acrylate / 2-
Ethylhexyl acrylate / acrylic acid (mass ratio 3
0: 15: 50: 5). [0037]Second polymer (1) PCL-H1P: crystalline polycaprolactone (Daicel
Chemical Industry, PLACCEL H1P, Mw = 25,000). (2) CrysP-1: polycaprolactone diol (Daice
Chemical Co., PLACCEL 240, Mw = 11,000) and isophorone
Polycaprolactone-based polyether reacted with isocyanate
Urethane (Mw = 28,000). (3) CrysP-2: Polyester polyol (Kuraray, K
Rare polyol O-2010, Mw = 7,000) and isophorone diiso
Polyester polyurethane reacted with cyanate
(Mw = 40,000). (4) CrysP-3: polycarbonate diol (Daicel
Chemical Industry, PLACCEL CD220, Mw = 7,000) and isophorone
Polycarbonate poly obtained by reacting with isocyanate
Urethane (Mw = 15,000). [0038]Third polymer (1) Poly-1: Polycarbonate diol (daicelized
Gaku Kogyo, PLACCEL CD220PL, Mw = 4,000) and isophorone
Polycarbonate poly obtained by reacting with isocyanate
Urethane (Mw = 37,000, Tg based on DSC = −37 ° C.). (2) Poly-2: polycaprolactone diol (Daicel
Chemical Industry, PLACCEL 205, Mw = 500) and isophorone diiso
Polycaprolactone-based polyurethane reacted with cyanate
Retane (Mw = 26,000, Tg based on DSC = -35 ° C.). (3) Poly-3: Polyester polyol (Kuraray, Kuraray
Polyol PMSA-2000) and isophorone diisocyanate
Polyester polyurethane (Mw = 38,
000, Tg based on DSC = -30 ° C).Crosslinking agent Isophthaloylbis (2-methylaziridine). [0039]2. Evaluation of film adhesive (1) Initial adhesive strength (including low temperature adhesive strength) Next, the above film adhesive is applied to a roller for about 2k.
g / cm^TwoSUS304 stainless steel while applying pressure
Laminated with a plate (JIS G 4305, thickness 0.8mm)
Was prepared. This sample is kept at 25 ° C., that is, room temperature for 24 hours.
After standing, at a speed of 300 mm / min.
At 180 ° C or 25 ° C or -5 ° C, respectively.
180 ° peel adhesion at that time (initial contact
(Force) was determined at each temperature. Table 1 shows the initial
Shows the adhesive strength. The film adhesives of Examples 1 to 5 are
3 By adding the polymer, that of Comparative Examples 1 and 2
Has a higher tack at room temperature than
Was. Also, the third polymer is effectively compatible with the first polymer.
That the third polymer is essentially a plasticizer
Was visually confirmed. (2) Ease of heating and re-peeling Place the above sample in the oven again at 80 ° C for 3 minutes.
After heating, remove from oven and leave at 25 ° C for 3 minutes
did. At this time, the first polymer, the second polymer and the third polymer
Visual confirmation that the polymers are compatible with each other
Was. Next, film adhesion at a speed of 300 mm / min.
The agent was peeled 180 ° from the sample at 25 ° C.
The 80 ° peel adhesion was determined. Also, place the sample in the oven
And left at 25 ° C for 24 hours.
Was measured for 180 ° peel adhesion. Table 1 shows the above 1
Shows 80 ° peel adhesion. [0042] [Table 1]From Table 1, it is found that Examples 1 to 5 and Comparative Example 1 were used.
And each of the film adhesives of Comparative Example 2 and 25 ° C.
Have a similar high initial adhesive strength
You. However, the film adhesives of Examples 1 to 5
While the adhesive strength is improved at a relatively low temperature of -5 ° C.
The film adhesives of Comparative Examples 1 and 2 have an adhesive strength
Is decreasing. In Comparative Examples 1 and 2, comparatively
Acrylic first polymer with high Tg is film
Occupying most of the adhesive reduces the low temperature adhesive strength
It is thought that it was. Furthermore, the files of Examples 1 to 5
Film adhesive maintains low adhesive strength even after 3 minutes of heating
It is clear that the film is easily removable again. More
Ming's film adhesive has high adhesive strength 24 hours after heating
And is useful as a heat activated adhesive.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4J040 CA071 CA072 CA081 CA082                       DF001 DF002 DF031 DF032                       ED002 EF001 EF002 EF111                       EF112 EF121 EF122 EF281                       EF282 EK031 EK032 EL022                       GA05 JA09 JB01 JB11 LA02                       LA06 LA08 MA02 MA04 MA05                       MA10 PA32 PA42

Claims (1)

Claims 1. An adhesive first polymer having a phenyl group and a hydroxyl group, a crystalline second polymer, and a polyester polyol having a glass transition point of -80 ° C to 0 ° C. And at least one non-crystalline third polymer selected from the group consisting of polycarbonate polyols and urethane compounds thereof.