WO2016021332A1 - Building member with pressure-sensitive adhesive sheet, and pressure-sensitive adhesive sheet for building member - Google Patents

Abstract

A building member (40) with a pressure-sensitive adhesive sheet, said member (40) comprising a building member (32) and a pressure-sensitive adhesive sheet for building members which has been laminated to the building member (32). The building member (40) with a pressure-sensitive adhesive sheet has an initial peel strength (N1), as measured after the member (40) was laminated to a basswood plywood and then allowed to stand at 23°C for 3 minutes, of 2.0 N/25 mm or less. In the member (40), the ratio of the aged peel strength (N2), as measured at 48 hours after the member (40) was laminated to the basswood plywood, to the initial peel strength (N1), N2/N1, is 1.5 or greater.

Description

Building member with adhesive sheet, and adhesive sheet for building member

The present invention relates to a building member with an adhesive sheet and an adhesive sheet for building members.

For architectural interior members such as wallpaper, decorative sheets, flooring materials, window films, floor sheets, etc., a method of applying a liquid adhesive to wallpaper or the like and sticking to walls or floors is usually used. However, when using adhesives, it is necessary to train with masking tape, prepare and apply the adhesive, clean the adhesive after construction, and peel off the masking tape. did. Further, if the construction technique is insufficient, the adhesive cannot be applied uniformly. For example, when wallpaper is applied, wrinkles may occur. Furthermore, there is a problem that it takes time for the adhesive to dry, and a room must be opened before drying.

On the other hand, an adhesive that improves the finish after construction by improving the coating stability has also been proposed (see Patent Document 1). However, the tasks and time required for preparation and cleanup before construction have not been solved. Moreover, the construction method which fixes a wallpaper with an adhesive is also known (refer patent document 2). In the construction method using an adhesive, it can be constructed with a simple method without wrinkles, but once pasted, it is difficult to rework (rework), and there is a problem that wrinkles are generated on the wallpaper at the time of peeling. It was.

JP2011-74693A JP 2004-250845 A

However, in the construction method using an adhesive, it can be constructed with a simple method without wrinkles, but once pasted, it is difficult to rework (rework) and wrinkles occur on the wallpaper when peeling. was there.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive sheet that contributes to improving the workability of building members such as wallpaper.

In order to solve the above-described problems, a building member with an adhesive sheet according to an aspect of the present invention includes a building member and an adhesive sheet for a building member bonded to the building member. The building material with an adhesive sheet has an initial peel force (N1) of 2.0 [N / 25 mm] or less after being allowed to stand for 3 minutes at 23 ° C. The ratio N2 / N1 between the peel force with time (N2) and the initial peel force (N1) after 48 hours has elapsed is 1.5 or more.

The aging peel force (N2) may be 3.0 [N / 25 mm] or more.

The building sheet pressure-sensitive adhesive sheet may have at least a pressure-sensitive adhesive layer containing a (meth) acrylic polymer having a weight average molecular weight of 10,000 or more and less than 50,000.

The building sheet pressure-sensitive adhesive sheet may have a base material and a pressure-sensitive adhesive layer laminated on at least one side of the base material.

The (meth) acrylic polymer may contain a monomer having a polyorganosiloxane skeleton as a monomer unit.

［式（１）（２）中、Ｒ３は水素またはメチルであり、Ｒ４はメチルまたは１価の有機基であり、ｍおよびｎは０以上の整数である］ The monomer having a polyorganosiloxane skeleton may be a polyorganosiloxane group-containing monomer having a functional group equivalent of 1000 g / mol or more and less than 15000 g / mol, represented by the following general formula (1) or (2).

[In the formulas (1) and (2), R3 is hydrogen or methyl, R4 is methyl or a monovalent organic group, and m and n are integers of 0 or more.]

The pressure-sensitive adhesive layer may contain 100 parts by mass of a polymer having a glass transition temperature of less than 0 ° C. and 0.1 to 20 parts by mass of a (meth) acrylic polymer.

The building member may be wallpaper, a decorative sheet, a flooring material, a window film, a skirting board, a waterproof sheet, a heat insulating sheet, a soundproof sheet, or a floor sheet.

Another aspect of the present invention is a pressure-sensitive adhesive sheet for building members used for building members with pressure-sensitive adhesive sheets.

Note that a combination of the above-described elements as appropriate can be included in the scope of the invention for which protection by patent is sought by this patent application.

According to the present invention, the workability of building members such as wallpaper can be improved.

It is a side view of the adhesive sheet which concerns on this Embodiment. It is the schematic diagram which looked at the adhesive sheet which concerns on an Example from the side. It is the schematic diagram which looked at the wallpaper with an adhesive sheet which concerns on an Example from the side. It is a schematic diagram for demonstrating a 180 degree | times peeling test. It is a schematic diagram which shows an example of a wrinkle. It is a schematic diagram for demonstrating a holding test. It is a figure for demonstrating the floating of a wallpaper.

[Building material with adhesive sheet]
The building member with a PSA sheet according to the present embodiment includes a building member and a PSA sheet for a building member bonded to the building member.

[Building materials]
Although it does not specifically limit as a building member, A wallpaper, a decorative sheet, a flooring material, a window film, a skirting board, a waterproof sheet, a heat insulation sheet, a soundproof sheet, a floor sheet etc. can be mention | raise | lifted.

The building material with an adhesive sheet according to the present embodiment has a low adhesive force and can be reworked immediately after being bonded to an adherend, and the adhesive force does not increase so much even with time at room temperature. Therefore, rework is possible even when the adhesive sheet is left on the adherend for a long time (for example, several minutes). That is, the pressure-sensitive adhesive sheet according to the present embodiment needs to be re-attached not only after re-attaching to the adherend but also in inspection after being left in the state of being attached to the adherend. It can easily cope with the case. Furthermore, no wrinkles are confirmed in the adhesive layer (adhesive layer) of the building member at the time of peeling (at the time of rework), and no irregularities appear on the surface of the building member even if the construction is performed again. Therefore, the building member with an adhesive sheet according to the present embodiment can be applied to various processes and uses in which the time for which the building member is left in the state of being bonded to an adherend is different. Moreover, since it can be reapplied for a long time, the manufacturing yield can be improved.

In addition, the building member with the pressure-sensitive adhesive sheet according to the present embodiment has a characteristic that adhesion reliability is high because the pressure-sensitive adhesive force in the initial state of bonding is small, but the pressure-sensitive adhesive force can be increased over time. .

The initial peel force (N1) immediately after bonding of the building member with the PSA sheet according to the present embodiment (after 3 minutes at 23 ° C.) is 180 ° when peeled at a tensile speed of 300 mm / min and a peel angle of 180 °. It can be evaluated by a peel adhesion test. The initial peel force (N1) is 2.0 N / 25 mm or less, preferably 1.5 N / 25 mm or less, more preferably 1.0 N / 25 mm or less (usually 0.1 N / 25 mm or more). . If the initial peel force (N1) is 2.0 N / 25 mm or less, it is easy to rework even a large-area building member, and wrinkles are not generated in the adhesive layer of the building member at the time of peeling (at the time of rework). It is not confirmed, and unevenness does not appear on the surface of the building member even if construction is performed again.

The peel strength with time (N2) after 48 hours from the pasting of the building material with an adhesive sheet according to the present embodiment is peeled off 180 ° when peeled at a pulling rate of 300 ° / min and a peel angle of 180 °. It can be evaluated by an adhesion test. The peel strength with time (N2) is preferably 3.0 N / 25 mm or more, more preferably 4.0 N / 25 mm or more, and further preferably 5.0 N / 25 mm or more (usually 15 N / 25 mm). Less than). If the peel strength with time (N2) is 3.0 N / 25 mm or more, the retainability to the adherend is ensured, and the building member does not fall.

The ratio N2 / N1 between the peel strength with time (N2) and the initial peel force (N1) after 48 hours has passed since the adhesive sheet-attached building member according to the present embodiment is bonded to the synthetic plywood is 1.5 or more. It is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more (usually 15.0 or less). If ratio N2 / N1 is 1.5 or more, the fixing performance (holding characteristic) of the building member after time can be satisfied.

[Adhesive composition]
The pressure-sensitive adhesive composition according to the embodiment includes a polymer (A) and a (meth) acrylic polymer (B).

Hereinafter, each component constituting the pressure-sensitive adhesive composition according to the embodiment will be described in detail.

[Polymer (A)]
The polymer (A) is a polymer having a glass transition temperature of less than 0 ° C. The polymer (A) is not particularly limited as long as the glass transition temperature is less than 0 ° C., and is generally used as an adhesive such as an acrylic polymer, a rubber polymer, a silicone polymer, a polyurethane polymer, and a polyester polymer. Various polymers can be used. In particular, when the polymer (B) is a (meth) acrylic polymer, an acrylic polymer that is easily compatible with the (meth) acrylic polymer and has high transparency is preferable.

The glass transition temperature (Tg) of the polymer (A) is less than 0 ° C., preferably less than −10 ° C., more preferably less than −40 ° C., and usually −80 ° C. or higher. When the glass transition temperature (Tg) of the polymer (A) is 0 ° C. or higher, the polymer is difficult to flow and the adhesive strength with time may be inferior.

The glass transition temperature is a nominal value described in literatures, catalogs, or the like, or a value calculated based on the following formula (X) (Fox formula).

_{1 / Tg = W 1 / Tg} 1 + W 2 / Tg 2 + ··· + Wn / Tg n (X)
[In the formula (X), Tg is the glass transition temperature (unit: K) of the polymer (A), and Tg _i (i = 1, 2,... N) is the glass transition when the monomer i forms a homopolymer. Temperature (unit: K), W _i (i = 1, 2,..., N) represents a mass fraction of all monomer components of monomer i. ]
The above formula (X) is a calculation formula when the polymer (A) is composed of n types of monomer components of monomer 1, monomer 2,..., Monomer n.

In the present specification, “glass transition temperature when homopolymer is formed” means “glass transition temperature of homopolymer of the monomer”, and may be referred to as a certain monomer (“monomer X”). ) Is the glass transition temperature (Tg) of a polymer formed using only the monomer component. Specifically, “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc, 1989) lists numerical values. In addition, the glass transition temperature (Tg) of the homopolymer which is not described in the said literature says the value obtained by the following measuring methods, for example. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 100 parts by weight of monomer X, 0.2 parts by weight of 2,2′-azobisisobutyronitrile, and ethyl acetate 200 as a polymerization solvent. Stirring is performed for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 63 ° C. and the reaction is carried out for 10 hours. Subsequently, it cools to room temperature and the homopolymer solution with a solid content concentration of 33 mass% is obtained. Next, this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of this test sample is weighed in an aluminum open cell, and a nitrogen atmosphere of 50 ml / min is used using a temperature modulation DSC (trade name “Q-2000”, manufactured by T.A. Instruments Inc.). Under the heating rate of 5 ° C./min, the reversing heat flow (specific heat component) behavior of the homopolymer is obtained. Referring to JIS-K-7121, the low temperature side baseline of the obtained Reversing Heat Flow and the straight line that is equidistant in the vertical axis from the straight line that extends the high temperature side baseline, and the stepwise change of the glass transition The temperature at the point where the partial curve intersects is the glass transition temperature (Tg) when the homopolymer is used.

The weight average molecular weight (Mw) of the polymer (A) is, for example, about 50,000 to 5,000,000. When the weight average molecular weight (Mw) is less than 50,000, the cohesive force of the pressure-sensitive adhesive is insufficient and the adhesion reliability may be inferior. On the other hand, when the weight average molecular weight (Mw) exceeds 5,000,000, the fluidity of the pressure-sensitive adhesive is lowered, and there are cases where the adhesive strength increases with time.

[Acrylic polymer]
Hereinafter, an acrylic polymer which is a preferred specific example of the polymer (A) will be described in detail.

The acrylic polymer is, for example, a polymer containing 50% by mass or more of (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms as a monomer unit. In addition, the acrylic polymer may have a configuration in which (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is used alone or in combination of two or more. The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods generally used as synthetic methods for acrylic polymers such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization are applied. Thus, the polymer can be obtained.

The proportion of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms is 50% by mass to 99.9% by mass with respect to the total amount of monomer components for preparing the acrylic polymer. %, Preferably 60 mass% to 98 mass%, more preferably 70 mass% to 95 mass%.

Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acryl Isopentyl acid, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) Isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth Undecyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid C _1-20 alkyl ester [preferably (meth) acrylic acid C _2-14 alkyl] such as octadecyl acid, isooctadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate Ester, more preferably (meth) acrylic acid C _2-10 alkyl ester] and the like. In addition, (meth) acrylic acid alkyl ester means acrylic acid alkyl ester and / or (meth) acrylic acid alkyl ester, and “(meth)...” Has the same meaning.

Acrylic polymers can be copolymerized with other (meth) acrylic acid alkyl esters as needed for the purpose of modifying cohesion, heat resistance, crosslinkability, etc. Monomer). Therefore, the acrylic polymer may contain a copolymerizable monomer together with the (meth) acrylic acid alkyl ester as the main component. As the copolymerizable monomer, a monomer having a polar group can be suitably used.

As a specific example of the copolymerizable monomer,
Carboxyl group-containing monomers such as acrylic acid, (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylate such as (meth) acrylate;
Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride;
Sulphonic acid groups such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Containing monomers;
Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di N, N-dialkyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) such as (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide Acrylamide, N-butyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl ( (Meth) acrylamide, N-methoxyethyl (meta) Acrylamide, N- butoxymethyl (meth) acrylamide, N- acryloyl morpholine, etc. (N- substituted) amide monomers;
Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide;
Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide;
Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers;
Vinyl esters such as vinyl acetate and vinyl propionate;
N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, Contains nitrogen such as N-vinylisothiazole and N-vinylpyridazine Ring-based monomer;
N-vinylcarboxylic acid amides;
Lactam monomers such as N-vinylcaprolactam;
Cyano-containing monomers such as acrylonitrile and (meth) acrylonitrile;
(Meth) acrylic such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Acid aminoalkyl monomers;
(Meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid propoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid ethoxypropyl ;
Styrene monomers such as styrene and α-methylstyrene;
Epoxy group-containing acrylic monomers such as (meth) glycidyl acrylate;
(Meth) acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth) acrylate, silicone (meth) acrylate and other heterocyclic rings, halogen atoms, silicon atoms and the like, acrylic ester monomers;
Olefin monomers such as isoprene, butadiene, isobutylene;
Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether;
Vinyl esters such as vinyl acetate and vinyl propionate;
Aromatic vinyl compounds such as vinyltoluene and styrene;
Olefins or dienes such as ethylene, butadiene, isoprene, isobutylene;
Vinyl ethers such as vinyl alkyl ethers;
Vinyl chloride;
Sulfonic acid group-containing monomers such as sodium vinyl sulfonate;
Imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide;
Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth) acrylate;
Acryloylmorpholine;
(Meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate and phenoxyethyl (meth) acrylate;
(Meth) acrylic acid ester obtained from terpene compound derivative alcohol;
Etc. These copolymerizable monomers can be used alone or in combination of two or more.

By containing 0.01% by mass or more of the copolymerizable monomer, it is possible to prevent the cohesive force of the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed of the acrylic pressure-sensitive adhesive composition from being lowered. Moreover, by making content of a copolymerizable monomer into 40 mass% or less, it can prevent that cohesion force becomes high too much and can improve the tuck feeling in normal temperature (25 degreeC).

The acrylic polymer may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive composition to be formed.

Examples of the polyfunctional monomer include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylol (meth) tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate Polyester acrylate, urethane acrylate, butyl diol (meth) acrylate, hexyl diol (meth) acrylate. Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. A polyfunctional monomer can be used individually or in combination of 2 or more types.

The amount of the polyfunctional monomer used varies depending on the molecular weight and the number of functional groups, but is 0.01% by mass to 3.0% by mass, preferably 0%, based on the total amount of monomer components for preparing the acrylic polymer. It is added in an amount of 0.02 mass% to 2.0 mass%, more preferably 0.03 mass% to 1.0 mass%.

When the amount of the polyfunctional monomer used exceeds 3.0% by mass based on the total amount of monomer components for preparing the acrylic polymer, for example, the cohesive force of the pressure-sensitive adhesive composition becomes too high, and the initial pressure-sensitive adhesive strength The suppression effect may be reduced. On the other hand, when the content is less than 0.01% by mass, for example, the cohesive force of the pressure-sensitive adhesive composition may be reduced, and the increase in the adhesive force over time may be insufficient.

When preparing an acrylic polymer, it is possible to easily form an acrylic polymer by using a curing reaction by heat or ultraviolet rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator). it can. A polymerization initiator can be used individually or in combination of 2 or more types.

Examples of the thermal polymerization initiator include azo polymerization initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis ( 2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine) dihydrochloride, etc.); peroxide polymerization initiators (eg, dibenzoyl peroxide, t-butylpermaleate, lauroyl peroxide, etc.) Redox polymerization initiators, and the like.

The amount of the thermal polymerization initiator used is not particularly limited, but for example, 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the monomer component for preparing the acrylic polymer. It mix | blends in the quantity in the range of the mass part.

The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive initiators. Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator An agent or the like can be used.

Specifically, examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- 1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisoin and the like can be mentioned. As the acetophenone photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [trade name: Irgacure 2959, manufactured by BASF Corp.], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [trade name: Darocur 1173, manufactured by BASF], methoxyacetophenone, and the like can be given. Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1- ON etc. are mentioned. Examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.

The benzoin photopolymerization initiator includes, for example, benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like are included.

Examples of the acylphosphine photopolymerization initiator include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis ( 2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1- Methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine Oxides, bis (2- Toxibenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2-methyl Propan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropane-1- Yl) phosphine oxide, bis (2,4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine oxide Bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis 2,6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide Bis (2,4,6-trimethylbenzoyl) -2,5-diisopropylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide, bis (2 4,6-trimethylbenzoyl) -4-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 3,5,6-tetramethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethylmethybenzoyl-2,4,6-trimethyl Benzoyl-n-butylphosphine oxide, bis (2,4,4 -Trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide, 1,10-bis [bis (2,4,6-trimethylbenzoyl) phosphine oxide] Examples include decane and tri (2-methylbenzoyl) phosphine oxide.

The amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the monomer component for preparing the acrylic polymer. In an amount within the range of parts.

Here, if the amount of the photopolymerization initiator used is less than 0.01 parts by mass, the polymerization reaction may become insufficient. When the usage-amount of a photoinitiator exceeds 5 mass parts, an ultraviolet-ray may not reach the inside of an adhesive layer because a photoinitiator absorbs an ultraviolet-ray. In this case, the polymerization rate is lowered, or the molecular weight of the produced polymer is reduced. And thereby, the cohesive force of the adhesive layer formed becomes low, and the adhesive force raise with time may become inadequate. In addition, a photopolymerization initiator can be used individually or in combination of 2 or more types.

In the present embodiment, the polymer (A) is a partial polymer (acrylic polymer syrup) obtained by irradiating a mixture of the monomer component and the polymerization initiator with ultraviolet rays (UV) to partially polymerize the monomer component. It can also be prepared as. A pressure-sensitive adhesive composition is prepared by blending the polymer (B) described later with an acrylic polymer syrup, and this pressure-sensitive adhesive composition is applied to a predetermined coated body and irradiated with ultraviolet rays to complete the polymerization. You can also. That is, the acrylic polymer syrup is a precursor of the polymer (A), and the polymer (B) blended with the acrylic polymer syrup also corresponds to the pressure-sensitive adhesive composition of the present embodiment.

[(Meth) acrylic polymer (B)]
The (meth) acrylic polymer (B) (hereinafter referred to as “polymer (B)” as appropriate) has a weight average molecular weight of 10,000 or more and less than 50,000. The (meth) acrylic polymer preferably contains a monomer having a polyorganosiloxane skeleton as a monomer unit.

The monomer (B1) having a polyorganosiloxane skeleton constituting the polymer (B) is not particularly limited, and any polyorganosiloxane skeleton-containing monomer can be used. Since the polyorganosiloxane skeleton-containing monomer has a low polarity derived from its structure, it actively promotes the uneven distribution of the polymer (B) on the surface of the adherend, and exhibits light release at the initial stage of bonding. .

［式（１）（２）中、Ｒ^３は水素またはメチルであり、Ｒ^４はメチルまたは１価の有機基であり、ｍおよびｎは０以上の整数である］ As a specific example of the polyorganosiloxane skeleton-containing monomer, for example, a polyorganosiloxane skeleton-containing monomer represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-174DX, X-22-2426, X-22-2475, KF-2012, etc. These may be used alone or in combination of two or more.

[In the formulas (1) and (2), R ³ is hydrogen or methyl, R ⁴ is methyl or a monovalent organic group, and m and n are integers of 0 or more.]

The functional group equivalent of the monomer (B1) having a polyorganosiloxane skeleton constituting the polymer (B) is 1000 g / mol or more and less than 15000 g / mol. When the functional group equivalent of the monomer (B1) having a polyorganosiloxane skeleton is less than 1000 g / mol, light peelability may not be exhibited, and adhesive strength may not be reduced at the initial stage of bonding. In addition, when the functional group equivalent of the monomer having a polyorganosiloxane skeleton is 15000 g / mol or more, the compatibility with the polymer (A) is remarkably deteriorated, and the adhesive force does not decrease at the initial stage of bonding to the adherend. Or, it may be inferior in increasing adhesive strength over time.

Here, “functional group equivalent” means the mass of the main skeleton (for example, polydimethylsiloxane) bonded per functional group. The title unit g / mol is converted to 1 mol of functional group. The functional group equivalent of the monomer having a polyorganosiloxane skeleton is calculated from, for example, the spectrum intensity of ¹ H-NMR (proton NMR) obtained by a nuclear magnetic resonance measuring apparatus (NMR).

^{In 1} H-NMR, the spectral intensity of H (for example, H of Si— (CH ₃ ) ₂ ) bonded to silicon of a siloxane structure via C, and the functional group C—CH ₃ H, SH H, or The ratio of the spectral intensity of H of C = CH ₂ is obtained.

The case where the spectral intensity ratio of H of Si— (CH ₃ ) _{2 having} a siloxane structure and the spectral intensity ratio of H of functional group C═CH ₂ will be described as an example. The ratio of the number of Si— (CH ₃ ) _{2 having} a siloxane structure and the number of functional groups C═CH ₂ is known.

Since the chemical formula of the siloxane structure and the chemical formula of the functional group are known in advance, from the ratio of the number of Si— (CH ₃ ) ₂ of the siloxane structure and the number of functional groups C═CH ₂ , The ratio (A / B) of the number A of siloxane structures having a — (CH ₃ ) ₂ bond and the number B of functional groups is known.

Since the molecular weight per siloxane structure having a Si— (CH ₃ ) ₂ bond (here, dimethylsiloxane) is known, the number A of the siloxane structure, the number of functional groups, The value obtained by multiplying the ratio (A / B) is the mass of the siloxane structure having a Si— (CH ₃ ) ₂ bond per functional group, that is, the mass of the main skeleton, and the mass is multiplied by the Avogadro number. The value becomes the functional group equivalent (g / mol).

In addition, when using the monomer which has 2 or more types of polyorganosiloxane frame | skeleton from which a functional group equivalent differs, the value which carried out arithmetic average can be used for the functional group equivalent. That is, it can be calculated by the following formula.
Functional group equivalent of monomer mixture (g / mol) = (Functional group equivalent of monomer 1 × Amount of monomer 1 added + Functional equivalent of monomer 2 × Amount of monomer 2 + ... + Functional equivalent of monomer n × Monomer n blending amount) / (monomer 1 blending amount + monomer 2 blending amount +... + Monomer n blending amount)

The content of the monomer (B1) having a polyorganosiloxane skeleton having a functional group equivalent of 1000 g / mol or more and less than 15000 g / mol is 5% by mass or more and 50% by mass or less with respect to all monomer components of the polymer (B). Yes, it is preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 30% by mass or less. When the content is less than 5% by mass, the adhesive strength may not decrease at the initial stage of bonding. On the other hand, when the content is more than 50% by mass, the adhesive strength with time may be poor.

The polymer (B) is selected from the group consisting of a monomer having a polyorganosiloxane skeleton, a (meth) acrylic monomer, a monomer having a polyoxyalkylene skeleton, a (meth) acrylic acid ester monomer, and a copolymerizable monomer. It may be a copolymer with one or more monomers.

Examples of such (meth) acrylic acid ester monomers include
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate , T-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) Octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as dodecyl acrylate;
(Meth) acrylic acid ester having an alicyclic hydrocarbon group such as dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
(Meth) acrylic acid ester obtained from terpene compound derivative alcohol;
Amide group-containing vinyl monomers such as acryloylmorpholine, dimethylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, isopropylacrylamide, and hydroxyethylacrylamide;
Lactam monomers such as N-vinylcaprolactam such as N-vinyl-2-caprolactam;
Etc. Such (meth) acrylic acid esters can be used alone or in combination of two or more.

The polymer (B) is obtained by copolymerizing other monomer components (copolymerizable monomers) copolymerizable with (meth) acrylic acid esters in addition to the (meth) acrylic acid ester component units. Is also possible. For example, in the polymer (B), a functional group having reactivity with an epoxy group or an isocyanate group may be introduced. Examples of such functional groups include a hydroxyl group, a carboxyl group, an amino group, an amide group, and a mercapto group, and a monomer having such a functional group is used in the production of the polymer (B) (copolymerization). )

As other monomer copolymerizable with (meth) acrylic acid ester,
Carboxyl group-containing monomers such as acrylic acid, (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate monomer;
(Meth) acrylic acid alkali metal salts and the like;
Di (meth) acrylic acid ester of ethylene glycol, di (meth) acrylic acid ester of diethylene glycol, di (meth) acrylic acid ester of triethylene glycol, di (meth) acrylic acid ester of polyethylene glycol, di (meta) of propylene glycol ) (Poly) oxyalkylene di (meth) acrylate monomers such as acrylate esters, di (meth) acrylate esters of dipropylene glycol, di (meth) acrylate esters of tripropylene glycol;
Polyvalent (meth) acrylate monomers such as trimethylolpropane tri (meth) acrylate;
Vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl halide compounds such as vinylidene chloride and 2-chloroethyl (meth) acrylate;
An oxazoline group-containing polymerizable compound such as 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline;
Aziridine group-containing polymerizable compounds such as (meth) acryloylaziridine and (meth) acrylic acid-2-aziridinylethyl;
Epoxy group-containing vinyl monomers such as allyl glycidyl ether, (meth) acrylic acid glycidyl ether, (meth) acrylic acid-2-ethylglycidyl ether;
Hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, adducts of lactones with 2-hydroxyethyl (meth) acrylate;
Fluorine-containing vinyl monomers such as fluorine-substituted (meth) acrylic acid alkyl esters;
Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride;
Aromatic vinyl compound monomers such as styrene, α-methylstyrene, vinyltoluene;
Reactive halogen-containing vinyl monomers such as 2-chloroethyl vinyl ether and monochloro vinyl acetate;
(Meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N An amide group-containing vinyl monomer such as ethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-acryloylmorpholine;
Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide;
Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide;
Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers;
N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole Nitrogen-containing heterocyclic monomers such as N-vinylisothiazole and N-vinylpyridazine;
N-vinylcarboxylic acid amides;
Lactam monomers such as N-vinylcaprolactam;
Cyanoacrylate monomers such as (meth) acrylonitrile;
(Meth) acrylic such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Acid aminoalkyl monomers;
Imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide;
Isocyanate group-containing monomers such as 2-isocyanatoethyl (meth) acrylate;
Organosilicon-containing vinyl monomers such as vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane;
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, (meta ) Hydroxyl-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxylauryl acrylate and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate;
(Meth) acrylic acid tetrahydrofurfuryl, fluorine atom-containing (meth) acrylate, silicone (meth) acrylate and other heterocyclic rings, halogen atoms, silicon atoms and the like, acrylic ester monomers;
Olefin monomers such as isoprene, butadiene, isobutylene;
Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether;
Olefins or dienes such as ethylene, butadiene, isoprene, isobutylene;
Vinyl ethers such as vinyl alkyl ethers;
Vinyl chloride;
Other examples include macromonomers having a radical polymerizable vinyl group at the terminal of a monomer obtained by polymerizing a vinyl group. These monomers can be copolymerized with the (meth) acrylic acid ester alone or in combination.

The weight average molecular weight of the polymer (B) is from 10,000 to less than 50,000, preferably from 12,000 to less than 50,000, and more preferably from 15,000 to less than 30,000. When the weight average molecular weight of the polymer (B) is 50000 or more, the adhesive strength at the initial stage of bonding does not decrease. Moreover, since it becomes low molecular weight as a weight average molecular weight is less than 10,000, the adhesive force of an adhesive sheet may not rise with time.

The measurement of the weight average molecular weight of the polymer (A) or the polymer (B) can be obtained by polystyrene conversion by gel permeation chromatography (GPC) method. Specifically, it is measured according to the method and conditions described in the examples described later.

The polymer (B) can be produced, for example, by polymerizing the above-described monomers by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization, a bulk polymerization, or the like.

In order to adjust the molecular weight of the polymer (B), a chain transfer agent can be used during the polymerization. Examples of the chain transfer agent used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, α-thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Thioglycolic acid esters such as thioglycolic acid ester of glycol, thioglycolic acid ester of neopentyl glycol, thioglycolic acid ester of pentaerythritol; α-methyl And styrene dimer.

The amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the monomer. More preferably, the content is 0.2 to 10 parts by mass. Thus, the (meth) acrylic-type polymer (B) of a suitable molecular weight can be obtained by adjusting the addition amount of a chain transfer agent. In addition, a chain transfer agent can be used individually or in combination of 2 or more types.

[Adhesive composition]
The pressure-sensitive adhesive composition contains the above-described polymer (A) and polymer (B as an essential component. The content of the polymer (B) is 0.1 mass relative to 100 parts by mass of the polymer (A). It is preferably no less than 20 parts by mass, but preferably no less than 0.3 parts by mass, no greater than 17 parts by mass, more preferably no less than 0.4 parts by mass and no greater than 15 parts by mass, and even more preferably no less than 0.5 parts by mass. Addition of the polymer (B) in excess of 20 parts by mass causes a decrease in the adhesive strength of the pressure-sensitive adhesive layer formed with the pressure-sensitive adhesive composition according to the present embodiment after aging. When the addition amount of the polymer (B) is less than 0.1 parts by mass, the effect of suppressing the adhesive force at the time of adhering the adherend is weak, and there may be a problem that rework cannot be performed.

The pressure-sensitive adhesive composition may contain various additives generally used in the field of the pressure-sensitive adhesive composition as optional components in addition to the polymer (A) and the polymer (B) described above. Such optional components include tackifier resins, crosslinking agents, catalysts, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, stabilizers, preservatives, antistatic agents, etc. Is exemplified. Conventionally known additives can be used as such additives.

In order to adjust the cohesive strength of the pressure-sensitive adhesive layer described later, a crosslinking agent can be used in addition to the various monomers described above. As the crosslinking agent, a commonly used crosslinking agent can be used. For example, an epoxy crosslinking agent, an isocyanate crosslinking agent, a silicone crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a silane crosslinking agent, an alkyl etherification agent. A melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. can be mentioned. In particular, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent can be preferably used. These compounds may be used alone or in combination of two or more.

Specifically, examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenyl (meth) diisocyanate, hydrogenated diphenyl (meth) diisocyanate. , Tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl (meth) triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane. Alternatively, a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule, specifically, 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent. Can do. These compounds may be used alone or in combination of two or more.

Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol propane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can do. These compounds may be used alone or in combination of two or more.

Examples of the metal chelate compound include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These compounds may be used alone or in combination of two or more.

The content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). preferable. When content is less than 0.01 mass part, the cohesion force of an adhesive composition may become small and it may be inferior to adhesive reliability. On the other hand, when the content exceeds 15 parts by mass, the cohesive force of the pressure-sensitive adhesive composition is large, the fluidity is lowered, and the increase in pressure-sensitive adhesive strength with time may be inferior.

The pressure-sensitive adhesive composition disclosed herein can further contain a crosslinking catalyst for causing any of the above-described crosslinking reactions to proceed more effectively. As such a crosslinking catalyst, for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst (for example, a tin-based catalyst such as dioctyltin dilaurate) is not particularly limited, and can be, for example, about 0.0001 parts by mass to 1 part by mass with respect to 100 parts by mass of the polymer (A). .

The tackifying resin is not particularly limited. For example, in addition to rosin tackifying resin, terpene tackifying resin, phenol tackifying resin, hydrocarbon tackifying resin, ketone tackifying resin, polyamide tackifying Examples thereof include resins, epoxy tackifying resins, and elastomer tackifying resins.

Examples of rosin-based tackifier resins include unmodified rosins such as gum rosin, wood rosin and tall oil rosin (raw rosin), and modified rosins modified by polymerization, disproportionation, hydrogenation, etc. Polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin and other chemically modified rosins), and various rosin derivatives.
Examples of the rosin derivative include:
A rosin phenolic resin obtained by thermally polymerizing rosins (unmodified rosin, modified rosin, various rosin derivatives, etc.) by adding phenol with an acid catalyst;
Ester compounds of rosin obtained by esterifying unmodified rosin with alcohol (unmodified rosin ester), modified rosins such as polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, alcohols Rosin ester resins such as modified rosin ester compounds esterified by (polymerized rosin ester, stabilized rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, partially hydrogenated rosin ester, etc.);
An unsaturated fatty acid-modified rosin resin obtained by modifying an unmodified rosin or a modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.) with an unsaturated fatty acid;
Unsaturated fatty acid-modified rosin ester resin obtained by modifying rosin ester resin with unsaturated fatty acid;
Carboxyl group in unmodified rosin, modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.), unsaturated fatty acid modified rosin resin and unsaturated fatty acid modified rosin ester resin Rosin alcohol resin obtained by reducing
Examples thereof include non-modified rosin, modified rosin, and metal salts of rosin resins (particularly rosin ester resins) such as various rosin derivatives.

Examples of terpene-based tackifier resins include terpene resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers, and modified terpene resins (phenol modified, aromatic modified, hydrogenated modified). Modified terpene resins such as terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, and the like.

Examples of phenolic tackifying resins include condensates of various phenols (eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc.) with formaldehyde (eg, alkylphenolic resin, xyleneformaldehyde). Resin), a resol obtained by addition reaction of the phenols and formaldehyde with an alkali catalyst, and a novolak obtained by a condensation reaction of the phenols and formaldehyde with an acid catalyst.

Examples of hydrocarbon tackifying resins (petroleum tackifying resins) include:
Aliphatic hydrocarbons such as aliphatic hydrocarbon resins [olefins and dienes having 4 to 5 carbon atoms (olefins such as butene-1, isobutylene, pentene-1; dienes such as butadiene, 1,3-pentadiene, isoprene, etc.) Polymers, etc.]
Aliphatic cyclic hydrocarbon resin [A so-called “C4 petroleum fraction” or “C5 petroleum fraction” is obtained by cyclization and dimerization and then polymerized, and a cyclodiene compound (cyclopentadiene, diene) Cyclopentadiene, ethylidene norbornene, dipentene, etc.) polymers or hydrogenated products thereof, and the following aromatic hydrocarbon resins and alicyclic hydrocarbon resins obtained by hydrogenating aromatic rings of aliphatic / aromatic petroleum resins, etc. ],
Aromatic hydrocarbon resins [polymers of vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (such as styrene, vinyltoluene, α-methylstyrene, indene, methylindene)],
Examples include aliphatic / aromatic petroleum resins (such as styrene-olefin copolymers), aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins, and the like.

Examples of commercially available polymerized rosin esters that can be preferably used include trade names “Pencel D-125”, “Pencel D-135”, “Pencel D-160”, “Pencel KK”, and “Pencel” manufactured by Arakawa Chemical Industries, Ltd. C ”and the like are exemplified, but not limited thereto.

Commercially available terpene phenolic resins that can be preferably used include trade names “YS Polystar S-145”, “YS Polystar G-125”, “YS Polystar N125”, and “YS Polystar U-115” manufactured by Yashara Chemical Co., Ltd. Examples include, but are not limited to, trade names “TAMANOL 803L” and “TAMANOL 901” manufactured by Arakawa Chemical Industries, Ltd., and “Sumilite Resin PR-12603” manufactured by Sumitomo Bakelite Co., Ltd.

[Adhesive layer and adhesive sheet]
Then, the structure of the adhesive sheet which has an adhesive layer containing the adhesive composition which has the above-mentioned composition is demonstrated.

The pressure-sensitive adhesive layer can be a cured layer of the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition to a suitable support (for example, coating / coating) and then appropriately performing a curing treatment. When performing 2 or more types of hardening processes (drying, bridge | crosslinking, superposition | polymerization, etc.), these can be performed simultaneously or in multiple steps. In a pressure-sensitive adhesive composition using a partial polymer (acrylic polymer syrup), typically, as the curing treatment, a final copolymerization reaction is performed (the partial polymer is subjected to a further copolymerization reaction). A complete polymer is formed). For example, if it is a photocurable adhesive composition, light irradiation is implemented. If necessary, curing treatment such as cross-linking and drying may be performed. For example, when it is necessary to dry with a photocurable adhesive composition, it is good to perform photocuring after drying. In the pressure-sensitive adhesive composition using a completely polymerized product, typically, as the curing treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary.

Application and coating of the pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. it can. The pressure-sensitive adhesive composition may be directly applied to the support to form a pressure-sensitive adhesive layer, or the pressure-sensitive adhesive layer formed on the release liner may be transferred to the support.

The pressure-sensitive adhesive layer has a solvent-insoluble component ratio of 20.0 mass% to 99.0 mass%, preferably 30.0 mass% to 90.0 mass%. If the solvent-insoluble component ratio is less than 20.0% by mass, the cohesive force may be insufficient, resulting in poor adhesion reliability. If the solvent-insoluble component ratio exceeds 99.0% by mass, the cohesive force becomes too high. In some cases, the increase in adhesive strength over time may be insufficient. In addition, the evaluation method of a solvent insoluble component rate is mentioned later.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but usually good adhesiveness can be realized by setting it to 3 μm to 200 μm, preferably 5 μm to 150 μm. If the thickness of the pressure-sensitive adhesive layer is less than 3 μm, the increase in adhesive strength over time may be inferior. On the other hand, if the thickness of the pressure-sensitive adhesive layer exceeds 200 μm, the effect of suppressing the adhesive force immediately after bonding may be insufficient. is there.

FIG. 1 is a side view of the pressure-sensitive adhesive sheet 10 according to the present embodiment. The pressure-sensitive adhesive sheet 10 shown in FIG. 1 includes a base material 12 and a pressure-sensitive adhesive layer 14 that is laminated on one side of the base material 12 and is a pressure-sensitive adhesive composition. The pressure-sensitive adhesive sheet 10 is provided with such a pressure-sensitive adhesive layer fixedly on at least one surface of the substrate 12, that is, without intention to separate the pressure-sensitive adhesive layer 14 from the substrate 12. The concept of the pressure-sensitive adhesive sheet referred to here may include what are called pressure-sensitive adhesive tapes, pressure-sensitive adhesive films, pressure-sensitive adhesive labels, and the like. Further, it may be cut into a suitable shape, punched out, or the like according to the intended use. The pressure-sensitive adhesive layer is not limited to those formed continuously, and may be a pressure-sensitive adhesive layer formed in a regular or random pattern such as a dot shape or a stripe shape.

As the support (base material), for example,
Polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer Polyolefin films such as polymers, ethylene / vinyl alcohol copolymers, polyester films such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate films, polystyrene films, nylon 6, nylon 6,6, partially aromatic polyamides, etc. Plastic films such as polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film;
Foam substrates such as polyurethane foam and polyethylene foam;
Kraft paper, crepe paper, Japanese paper, etc .;
Cotton, soft cloth, etc .;
Nonwoven fabrics such as polyester nonwoven fabrics and vinylon nonwoven fabrics;
Metal foil such as aluminum foil and copper foil;
Can be appropriately selected and used depending on the application of the adhesive tape.

In addition, the support may be released with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., and antifouling treatment, acid treatment, alkali treatment, primer treatment. Further, easy adhesion treatment such as corona treatment, plasma treatment, and ultraviolet treatment can be performed. The thickness of the support can be appropriately selected depending on the purpose, but is generally about 5 μm to 200 μm (typically 10 μm to 100 μm).

For the above-mentioned support, if necessary, silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release with silica powder and antifouling treatment, acid treatment, alkali treatment, primer treatment, Anti-adhesive treatment such as corona treatment, plasma treatment and ultraviolet treatment, coating type, kneading type, vapor deposition type and the like can also be carried out.

In the pressure-sensitive adhesive sheet of this embodiment, a release liner can be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface as necessary.

The material constituting the release liner includes paper and plastic film, but a plastic film is preferably used because of its excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

The thickness of the release liner is usually about 5 μm to 200 μm, preferably about 10 μm to 100 μm. It is preferable for it to be in the above-mentioned range since it is excellent in workability for bonding to the pressure-sensitive adhesive layer and workability for peeling from the pressure-sensitive adhesive layer. For the release liner, if necessary, release agent and antifouling treatment with silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, coating type, kneading type, vapor deposition An antistatic treatment such as a mold can also be performed.

Hereinafter, examples of the present invention will be described. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

(Preparation of adhesive polymer)
(Polymer A1)
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 95 parts by mass of n-butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 2,2 ′ as a polymerization initiator -Add 0.2 parts by weight of azobisisobutyronitrile and 157 parts by weight of toluene, introduce nitrogen gas with gentle stirring, and perform the polymerization reaction for 6 hours while keeping the liquid temperature in the flask at around 65 ° C. A polymer A1 having a weight average molecular weight of 500,000 was obtained.

(Polymer A2)
In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, 100 parts by mass of 2-ethylhexyl acrylate (2EHA), 5 parts by mass of 4-hydroxybutyl acrylate (4HBA), acrylic acid (AA) 0.01 parts by weight, 0.22 parts by weight of 2,2′-azobisisobutyronitrile and 157 parts by weight of ethyl acetate as a polymerization initiator are charged, and a polymerization reaction is carried out for 6 hours. A polymer having a weight average molecular weight of 540,000 A2 was obtained.

(Preparation of (meth) acrylic polymer (MMA / BMA / 2EHMA / X-22-174ASX / KF-2012 = 40/20/20 / 8.7 / 11.3) as component (B))
100 parts by mass of toluene, 40 parts by mass of methyl (meth) acrylate (MMA), 20 parts by mass of butyl (meth) acrylate (BMA), 20 parts by mass of 2-ethylhexyl (meth) acrylate (2-EHMA), 900 g functional group equivalent / Mol of polyorganosiloxane skeleton-containing (meth) acrylate monomer (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts by mass, functional group equivalent of 4600 g / mol of polyorganosiloxane skeleton 11.3 parts by mass of (meth) acrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.51 part by mass of methyl thioglycolate as a chain transfer agent were introduced into a stirring blade, a thermometer, and nitrogen gas introduced. A four-necked flask equipped with a tube, a condenser, and a dropping funnel was charged. And after stirring at 70 degreeC in nitrogen atmosphere for 1 hour, after adding 0.2 mass part of azobisisobutyronitrile as a thermal polymerization initiator and making it react at 70 degreeC for 2 hours, a thermal polymerization initiator Was added at 0.1 parts by mass of azobisisobutyronitrile, followed by reaction at 80 ° C. for 5 hours. The obtained (meth) acrylic polymer (B) had a weight average molecular weight of 22,000. The arithmetic average of the functional group equivalent of the monomer having a polyorganosiloxane skeleton used was 2990.

<Measurement of molecular weight>
The weight average molecular weight of the polymer was measured using a GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Corporation). The measurement conditions were as follows, and the molecular weight was determined by standard polystyrene conversion.
Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
Sample injection volume: 10 μl
・ Eluent: THF
・ Flow rate: 0.6ml / min
・ Measurement temperature: 40 ℃
·column:
Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1 piece)
・ Detector: Differential refractometer (RI)

(Example 1)
(Preparation of adhesive composition)
After adding 3 parts by mass of the above-mentioned (meth) acrylic polymer (B) and 0.1 part by mass of Coronate HX as a cross-linking agent to 100 parts by mass of the above-described polymer A1, An adhesive composition (1) was prepared.

(Strong adhesive pressure-sensitive adhesive composition)
After adding 0.1 parts by mass of coronate HX as a crosslinking agent to 100 parts by mass of the above-described polymer A1, a strongly adhesive pressure-sensitive adhesive composition (2) was prepared by uniformly mixing them.

(Preparation of adhesive sheet)
Drawing 2 is a mimetic diagram which looked at pressure sensitive adhesive sheet 20 concerning an example from the side. The pressure-sensitive adhesive composition (1) described above was applied to the release-treated surface of a 38 μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) 28 having one surface peel-treated with silicone, and 3 ° C. at 130 ° C. The pressure-sensitive adhesive layer 22 was obtained by partial drying.

Separately, the strongly adhesive pressure-sensitive adhesive composition (2) was applied to the release-treated surface of a polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics Co., Ltd.) 30 having a thickness of 38 μm, which was peeled on one side with silicone, and 130 ° C. Was dried for 3 minutes to obtain a strong pressure-sensitive adhesive layer 24 having a thickness of 40 μm.

Next, the pressure-sensitive adhesive layer 22 and the strong pressure-sensitive adhesive layer 24 of Example 1 were bonded to both surfaces of the nonwoven fabric 26, respectively. Both pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet 20 are protected as they are by the release liners 28 and 30 used for producing the pressure-sensitive adhesive sheet 20.

FIG. 3 is a schematic view of the wallpaper with the adhesive sheet according to the embodiment as seen from the side. The separator (the release liner 30 on the side of the strong adhesive layer 24) of the pressure-sensitive adhesive sheet 20 produced as described above is peeled off, and the back side of the strong adhesive layer 24 and the building member 32 (wallpaper 1: LL-3001 manufactured by Lilycala). The wallpaper with an adhesive sheet which is one of the building members 40 with an adhesive sheet was obtained by bonding.

Table 1 shows the composition of the pressure-sensitive adhesive composition and the specifications of the pressure-sensitive adhesive sheet according to each example and each comparative example.

(Example 4, Comparative Examples 1, 3, 5, 6)
Each pressure-sensitive adhesive sheet of Example 4 and Comparative Examples 1, 3, 5, and 6 was prepared by the same method as in Example 1 by preparing a pressure-sensitive adhesive composition in the same manner as in Example 1 with the composition shown in Table 1. .

(Examples 2, 6, and 7)
The pressure-sensitive adhesive sheet separator (stripping liner 30 on the side of the strong pressure-sensitive adhesive layer 24) prepared in the composition of Table 1 was peeled off, and the strong pressure-sensitive adhesive layer 24 and the building member 32 (wallpaper 2: WallBask 2012 7812229 manufactured by Rasch) were bonded together. A wallpaper with an adhesive sheet (building member 40 with an adhesive sheet) was obtained.

(Examples 3 and 5, Comparative Examples 2 and 4)
The separator (the release liner 30 on the side of the strong pressure-sensitive adhesive layer 24) of the pressure-sensitive adhesive sheet produced with the composition shown in Table 1 is peeled off, and the strong pressure-sensitive adhesive layer 24 and the building member 32 (flooring material: cushioning floor CF sheet-H, manufactured by Toli Co., Ltd.) The back surface of the surface deco Moroccan tile was bonded to obtain a flooring material with an adhesive sheet (building member 40 with an adhesive sheet).

(Comparative Example 7)
A double-sided tape (manufactured by Nitto Denko Corporation, No. 5000NS) was bonded to the above-described wallpaper 1 as the building member 32 to prepare a wallpaper with an adhesive sheet (building member 40 with an adhesive sheet).

(Comparative Example 8)
Apply the starch-based adhesive (made by Asahi Pen Co., Ltd., standard type glue paper paste) to the above-mentioned wallpaper 1 as the building member 32 with a roller so as to have an application amount of 120 g / m ² (wet). I got a wallpaper with drugs.

(Test method)
[180 ° peel adhesion test]
What cut | disconnected the building member 40 with an adhesive sheet which concerns on each Example and each comparative example to width 25mm and length 100mm was used as the test piece. As the adherend 42, ordinary plywood (sina plywood) such as Type 1 and Class 2 specified by the Japanese Agricultural and Forestry Standard (JAS) was used. And the peeling liner 28 (polyester film) of the building member 40 with an adhesive sheet was peeled off, and the 2 kg roller was reciprocated, and the adhesive surface 22a of the building member 40 with an adhesive sheet was stuck on the adherend.

After pasting the building material 40 with the adhesive sheet on the normal plywood, it was left for 3 minutes, 30 minutes and 48 hours in an environment of 23 ° C. (initial conditions). And about the building member 40 with an adhesive sheet in each time, the other end of an adhesive sheet is peeled in the peeling direction of 180 degree | times at a speed | rate of 300 mm / min, and the adhesive force (resistance force) with respect to the adherend at that time (unit: N / 25 mm). The initial condition adhesive strength (N1) is 1.0 [N / 25 mm] or less, and the adhesive strength (N2) after 48 hours is 2.0 [N / 25 mm] or more as good (◯). did. FIG. 4 is a schematic diagram for explaining the 180 degree peel test.

[Measurement of wrinkles generated in the adhesive layer of building materials during peeling (rework)]
When wrinkles occur in the adhesive layer during rework, irregularities occur on the surface of the building member after rework. Therefore, the wrinkles 44 generated in the pressure-sensitive adhesive layer 22 of the building member 32 during the above peeling test (after 3 minutes) were visually observed. Those in which wrinkles did not occur were evaluated as good (◯), and those in which wrinkles occurred were determined as poor (×). FIG. 5 is a schematic diagram showing an example of wrinkles.

[Retention test]
FIG. 6 is a schematic diagram for explaining a holding test. As shown in FIG. 6, both ends of the plywood 46 to which the wallpaper with the pressure-sensitive adhesive sheet (building member 40 with the pressure-sensitive adhesive sheet) was bonded were fixed so that the pattern surface of the wallpaper faced downward and left for one week. What did not fall was made into favorable ((circle)), and what fell was made into defect (x). Further, the floating around 3 minutes after the adhesion was measured. FIG. 7 is a diagram for explaining the floating of the wallpaper.

[Glue protruding]
After bonding with a 2 kg roller, the adhesive protruding from between the wallpaper and the plywood was visually observed. The case where the adhesive did not protrude was evaluated as good (◯), and the case where the adhesive protruded was determined as poor (×).

Table 2 shows the results of the above tests.

As shown in Table 2, the building materials with pressure-sensitive adhesive sheets according to Examples 1 to 7 and Comparative Examples 5, 6 and 8 were 180 ° after being allowed to stand for 3 minutes in an environment of 23 ° C. after being bonded to the plywood. The initial adhesive strength (N1) according to the peel adhesive strength test is 2.0 N / 25 mm or less, and no wrinkle is confirmed on the adhesive layer of the building member at the time of peeling (at the time of rework). Unevenness does not appear on the surface of the member. However, the building material with an adhesive sheet according to Comparative Examples 1 to 4 and 7 having an initial adhesive strength (N1) of 2.0 N / 25 mm or more is large in order to peel off the building member with an adhesive sheet once attached to the Chinese plywood. Power is required. Therefore, wrinkles are generated in the adhesive layer, which is not preferable from the viewpoint of re-sticking (reworkability).

In addition, the wallpaper with the pressure-sensitive adhesive sheet according to Examples 1 to 7 has a ratio N2 / N1 between the peel strength with time (N2) and the initial peel strength (N1) of 2.0 or more, and The fixing performance (holding characteristics) can be satisfied. However, as for the building member with an adhesive sheet which concerns on the comparative examples 5 and 6, ratio N2 / N1 is all less than 2.0, and does not satisfy the fixing performance (holding characteristic) of the building member after time passage.

In addition, the wallpaper which concerns on the comparative example 8 is what apply | coated the adhesive agent directly, About each of ratio N2 / N1 of initial stage peeling force (N1), time-dependent peeling force (N2), and initial stage peeling force (N1), Although satisfying the desired value, since the paste protrudes, improvement in workability as in the building member with the pressure-sensitive adhesive sheet according to Examples 1 to 7 cannot be achieved.

10 Adhesive Sheets, 12 Substrates, 14 Adhesive Layers, 20 Adhesive Sheets, 22 Adhesive Layers, 22a Adhesive Surface, 24 Strong Adhesive Layers, 26 Nonwoven Fabrics, 28, 30 Release Liner, 32 Building Members, 40 Adhesive Sheeted Architecture Element.

The present invention can be used for building members with pressure-sensitive adhesive sheets and pressure-sensitive adhesive sheets for building members.

Claims (9)

Building materials,
An adhesive sheet for building members bonded to the building member;
A building member with an adhesive sheet comprising
The initial peel force (N1) after standing for 3 minutes at 23 ° C. after being bonded to a Chinese plywood is 2.0 [N / 25 mm] or less,
A building member with an adhesive sheet, wherein the ratio N2 / N1 between the peel strength with time (N2) and the initial peel force (N1) after 48 hours from pasting to the Chinese plywood is 1.5 or more. The building member with a pressure-sensitive adhesive sheet according to claim 1, wherein the peel strength with time (N2) is 3.0 [N / 25 mm] or more. The building sheet pressure-sensitive adhesive sheet is
The building member with an adhesive sheet according to claim 1 or 2, further comprising an adhesive layer containing a (meth) acrylic polymer having a weight average molecular weight of 10,000 or more and less than 50,000. The building sheet pressure-sensitive adhesive sheet is
A substrate;
The pressure-sensitive adhesive layer laminated on at least one side of the substrate;
The building member with the pressure-sensitive adhesive sheet according to claim 3, comprising: The building member with an adhesive sheet according to claim 3 or 4, wherein the (meth) acrylic polymer contains a monomer having a polyorganosiloxane skeleton as a monomer unit. The monomer having a polyorganosiloxane skeleton is a polyorganosiloxane group-containing monomer represented by the following general formula (1) or (2) and having a functional group equivalent of 1000 g / mol or more and less than 15000 g / mol. The building member with an adhesive sheet according to claim 5.

[In the formulas (1) and (2), R ³ is hydrogen or methyl, R ⁴ is methyl or a monovalent organic group, and m and n are integers of 0 or more.] The pressure-sensitive adhesive layer is
100 parts by mass of a polymer having a glass transition temperature of less than 0 ° C.,
0.1 to 20 parts by mass of the (meth) acrylic polymer,
The building member with an adhesive sheet according to any one of claims 3 to 6, characterized by comprising: The said building member is wallpaper, a decorative sheet, a flooring material, a window film, a skirting board, a waterproof sheet, a heat insulation sheet, a soundproof sheet, or a floor sheet, The one of Claim 1 thru | or 7 characterized by the above-mentioned. Building material with adhesive sheet. A building material pressure-sensitive adhesive sheet used for the building material with a pressure-sensitive adhesive sheet according to any one of claims 1 to 8.

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