JP5144898B2 - Adhesive product with release substrate - Google Patents

Description

  The present invention relates to an adhesive product with a release agent. More specifically, the present invention relates to a pressure-sensitive adhesive product with a release substrate, wherein the pressure-sensitive adhesive composition contains a polyoxyalkylene polymer having an alkenyl group, a compound having a hydrosilyl group, and a hydrosilylation catalyst.

  A curable composition obtained by reacting a polyoxypropylene-based polymer having an alkenyl group and a compound having a hydrosilyl group in the presence of a platinum catalyst has been proposed as a pressure-sensitive adhesive composition exhibiting suitable properties as a pressure-sensitive adhesive (for example, Patent Documents 1 and 2). When selling as a product as an adhesive product, in many cases, as a protective layer of the adhesive layer, a form in which a surface treatment agent exhibiting peelability to the adhesive layer is applied with various substrates It is desirable to do.

A thermosetting silicone is generally used as a surface treatment agent for a release substrate currently used. When using a commercially available thermosetting silicone release agent as a surface treatment for various release substrates, and when using a release film for an adhesive composition based on an acrylic polymer When the pressure-sensitive adhesive is cured on release paper, the pressure-sensitive adhesive layer exhibits suitable peelability. However, when used for a pressure-sensitive adhesive composition containing a polyoxypropylene-based polymer, when the pressure-sensitive adhesive is cured on a release paper, the pressure-sensitive adhesive layer does not exhibit suitable releasability, The performance of the pressure-sensitive adhesive cannot be exhibited sufficiently. In addition, when a film such as polyethylene terephthalate is used as a release substrate without a release treatment agent for a pressure-sensitive adhesive composition containing a polyoxypropylene polymer, the release force is high and it can be suitably used as a release paper. Can not.
JP2003-292926 WO2005 / 033239

  The present invention provides a pressure-sensitive adhesive with a release substrate that does not inhibit the expression of pressure-sensitive adhesive properties of a pressure-sensitive adhesive composition obtained by reacting a polyoxypropylene polymer having an alkenyl group and a compound having a hydrosilyl group in the presence of a platinum catalyst. The purpose is to provide drug products.

  As a result of various studies, the present inventor has irradiated the composition (C) comprising the cationic polymerizable epoxy group-containing silicone resin (A) and the cationic polymerization initiator (B) as a release agent layer of the release substrate with ultraviolet rays. By using the cured product obtained as a surface treatment agent for the base material, the polyoxyalkylene polymer (D) having an alkenyl group, the compound (E) having a hydrosilyl group, and the hydrosilylation catalyst (F) as essential components The present invention has been found to exhibit good peeling properties with respect to the resulting pressure-sensitive adhesive composition (G).

  The pressure-sensitive adhesive product with a release substrate of the present invention uses an exfoliation substrate having a composition comprising a cationic polymerizable epoxy group-containing silicone resin and a cationic polymerization initiator as a release substrate in the release layer. Increases convenience when using the pressure-sensitive adhesive as various pressure-sensitive adhesive products by exhibiting suitable peelability for the pressure-sensitive adhesive composition containing the polyoxypropylene polymer and the compound having a hydrosilyl group as essential components. .

  The cationically polymerizable epoxy group-containing silicone resin as component (A) of the present invention is a polyorganosiloxane having an epoxy functional group in the molecule. The main chain skeleton of the polyorganosiloxane may be linear, branched, or a mixture thereof. The type of epoxy functional group contained in the polyorganosiloxane is not particularly limited as long as ring-opening cationic polymerization proceeds with a cationic polymerization initiator. Specific examples include a γ-glycidyloxypropyl group, a β- (3,4-epoxycyclohexyl) ethyl group, a β- (4-methyl-3,4-epoxycyclohexyl) propyl group, and the like. Such a cationically polymerizable epoxy group-containing silicone resin is commercially available, and examples thereof include a product name “Silicolyse POLY200” manufactured by Rhodia.

The cationic polymerization initiator as the component (B) of the present invention serves as an initiator for ring-opening polymerization of polyorganosiloxane having an epoxy functional group in the molecule, and various known onium salt photoinitiators. The agent can be used. Specific examples include (R) ₂ I ⁺ X ⁻ , ArN ₂ ⁺ X ⁻ , (R) ₃ S ⁺ X ⁻ , (R represents an alkyl group and / or aryl group, Ar represents an aryl group, X ⁻ represents [ B (C ₆ H ₅ ) ₄ ] ⁻ , [B (C ₆ F ₅ ) ₄ ] ⁻ , [B (C ₆ H ₄ CF ₃ ) ₄ ] ⁻ , [(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ , [C ₆ F ₅ BF ₃ ] ⁻ , [B (C ₆ H ₃ F ₂ ) ₄ ] ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , HSO ₄ ⁻ , or ClO ₄ ^- etc.)). Such cationic polymerization initiators are commercially available, and examples thereof include a product name “Silicolyse CATA211” manufactured by Rhodia.

The amount of the onium salt photoinitiator used is not particularly limited, but is preferably about 0.3 to 0.8 parts by weight with respect to 100 parts by weight of the polyorganosiloxane. If the amount used is less than 0.3 parts by weight, the silicone release layer may be insufficiently cured. Moreover, when larger than 0.8 weight part, coloring may be caused to a peeling base material, and it is not preferable from impairing the external appearance of the adhesive product using this peeling base material. The content of the cationic polymerization initiator (B) per 1 m ² of the release agent layer is preferably 0.8 to 3.5 mg. If the content is less than 0.8 mg, the silicone release layer may be insufficiently cured. Moreover, when larger than 3.5 mg, it may cause coloring to a peeling base material, and is unpreferable from impairing the external appearance of the adhesive product using this peeling base material.

  Various known photosensitizers may be used in combination in order to improve the reactivity of the onium salt initiator. Specific examples of the photosensitizer include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone etc. are mentioned.

  In consideration of the compatibility and uniform mixing of the cationic polymerizable epoxy group-containing silicone resin (A) component of the present invention and the cationic polymerization initiator component (B), the cationic polymerization initiator is organic. It is preferable to dissolve or disperse in a solvent and mix with the cationically polymerizable epoxy group-containing silicone resin.

  The composition (C) of the present invention may contain various known additives, for example, polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, solvents, antifoaming agents, leveling agents, pigments and the like as necessary. It can also be added. In some cases, a silicon compound or the like may be contained within a range not departing from the object of the present invention.

  When applying the composition (C) of the present invention to a substrate, the composition (C) may be applied without a solvent, or the composition (C) may be dissolved in a solvent and applied. . Specific examples of the solvent include toluene, xylene, hexane, heptane, isopropanol, ethyl acetate and the like. When the composition (C) is dissolved in a solvent, these solvents may be used alone or in combination of two or more. In order to uniformly apply a thin film on the film substrate, it is preferable to apply the solvent by dissolving it with a solvent.

There is no restriction | limiting in particular as a polyoxyalkylene type polymer which has an alkenyl group which is (D) component of this invention, Various things can be used. Specifically, the polymer main chain has a repeating unit represented by the general formula (1). General formula (1):
-R ¹ -O- (1)
(Wherein R ¹ is a divalent alkylene group)
R ¹ in the general formula (1) is preferably a linear or branched alkylene group having 1 to 14, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (1) include —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H _{5 ) O -, - CH 2 C} (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, from the viewpoint of availability and workability, a polymer having —CH ₂ CH (CH ₃ ) O— as the main repeating unit is preferred. The main chain of the polymer may contain a repeating unit other than the oxyalkylene group. In this case, the total of oxyalkylene units in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

  The structure of the component (D) polymer may be a linear polymer or a branched polymer, or a mixture thereof, but in order to obtain good adhesion, the linear polymer is 50 It is preferable to contain it by weight% or more.

  The molecular weight of the component (D) polymer is preferably 1,000 to 70,000 in terms of number average molecular weight, more preferably 6,000 to 50,000, and particularly preferably 10,000 to 30,000. If the number average molecular weight is less than 1,000, the resulting cured product tends to be too brittle and good adhesive properties cannot be obtained. On the other hand, if the number average molecular weight exceeds 50,000, the viscosity becomes too high and the workability is remarkably lowered, which is not preferable. The number average molecular weight can be measured by various methods, but usually conversion from a terminal group analysis of a polyoxyalkylene polymer or measurement by a gel permeation chromatography (GPC) method is common.

Although there is no restriction | limiting in particular as an alkenyl group in (D) component, The alkenyl group shown by following General formula (2) is used suitably. General formula (2):
^{_{H 2 C = C (R 2}} ) - (2)
(Wherein R ² is hydrogen or a methyl group)
Although there is no restriction | limiting in particular as a coupling | bonding mode to the polyoxyalkylene type polymer of an alkenyl group, For example, the direct coupling | bonding of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond etc. are mentioned.

As a specific example of the polymer of component (D), general formula (3):
_{{H 2 C = C (R} 3) -R 4 -O} aR 5 (3)
(In the formula, R ³ is hydrogen or a methyl group, R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and one or more ether groups may be contained, R ⁵ is polyoxy An alkylene-based polymer residue, and a is a positive integer). R ⁴ is _{specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, - CH 2 CH 2 CH 2 CH 2 —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — and the like can be mentioned. From the viewpoint of ease of synthesis, —CH ₂ — is preferable.

Other specific examples of the polymer of component (D) are those of the general formula (4):
_{{H 2 C = C (R} 3) -R 4 -OC (= O)} aR 5 (4)
(Wherein R ³ , R ⁴ , R ⁵ and a are the same as above), and a polymer having an ester bond.

Further, the following general formula (5):
{H ₂ C = C (R ³ )} a R ⁵ (5)
(Wherein R ³ , R ^5, and a are the same as those described above). Furthermore, the following general formula (6):
_{{H 2 C = C (R} 3) -R 4 -OC (= O) O} aR 5 (6)
A polymer having a carbonate bond represented by the formula (wherein R ³ , R ⁴ , R ⁵ and a are the same as above) is also included.

  The polymerization method of the polyoxyalkylene polymer (D) is a normal polymerization method of oxyalkylene (anionic polymerization method using caustic alkali) disclosed in JP-A-50-13396, etc., and JP-A-50-149797. A polymerization method using a chain extension reaction method using this polymer as a starting material, a polymerization method using a cesium metal catalyst disclosed in Japanese Patent Application Laid-Open No. 7-179597, Japanese Patent Application Laid-Open No. 61-197631, Polymerization method using porphyrin / aluminum complex catalyst disclosed in JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, disclosed in JP-B-46-27250 and JP-B-59-15336 A polymerization method using a composite metal cyanide complex catalyst, a catalyst comprising a polyphosphazene salt disclosed in JP-A-10-273512, etc. It can be obtained by that polymerization.

  Practically, a method using a double metal cyanide complex catalyst is preferable from the viewpoint of catalyst availability and polymerization stability. A known method can be used as a method for producing the double metal cyanide complex catalyst. For example, U.S. Pat. Nos. 3,278,457, 3,278,459, 5,891,818, 5,767,323, 5,767,323, 5,536,883 No. 5,482,908, No. 5,158,922, No. 4,472,560, No. 6,063,897, No. 5,891,818, No. 5,627,122, The methods described in JP-A-5,482,908, JP-A-5,470,813, JP-A-5,158,922 and the like are preferable.

  The method for synthesizing the polyoxyalkylene polymer (D) having an alkenyl group includes a normal polymerization method (anionic polymerization method using caustic alkali) for producing the polyoxyalkylene polymer, and using this polymer as a raw material. In addition to the chain extension reaction methods described above, JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, JP-B-46-27250, and JP-B-59 It can be obtained by the method described in No. 15336.

  Various methods can be used for introducing an alkenyl group into the polyoxyalkylene polymer. For example, it can be introduced by copolymerization of a monomer having an alkenyl group such as allyl glycidyl ether and an oxyalkylene monomer. In addition, by reacting an oxyalkylene polymer having a functional group such as a hydroxyl group or an alkoxide group on the main chain or side chain with an organic compound having a functional group and an alkenyl group reactive to these functional groups, Alkenyl groups can be introduced into the main chain or side chain. In particular, when an alkenyl group is present at the end of the main chain of the polymer, the effective network chain length in the cured product is increased, and thus a cured product having excellent mechanical properties can be obtained.

  Examples of the organic compound having a functional group and an alkenyl group having reactivity with the above functional group include those having 3 to 20 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride or acrylic acid bromide. Saturated fatty acid acid halide, acid anhydride, allyl chloroformate, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl ( Chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

  The alkenyl group should be present in at least one, preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2 in one molecule of the polymer (D). When the number of alkenyl groups contained in one molecule of the polymer (D) is less than 1, curability may be insufficient. Further, when the number of alkenyl groups contained in one molecule increases, the network structure becomes too dense, so that the adhesive property is lowered, and when the number is 5 or more, good adhesive property is not exhibited.

（式中、２≦ｂ＋ｃ≦５０、２≦ｂ、０≦ｃである。Ｒは、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）、

（式中、０≦ｄ＋ｅ≦５０、０≦ｄ、０≦ｅである。Ｒは、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）、又は、

（式中、３≦ｆ＋ｇ≦２０、２≦ｆ、０≦ｇ＜１８である。Ｒは、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）等で示される鎖状又は環状のもの等が挙げられる。 The compound containing a hydrosilyl group as the component (E) in the present invention can be used without particular limitation as long as it has a hydrosilyl group. From the viewpoint of availability of raw materials and compatibility with the component (D), organohydrogenpolysiloxanes modified with organic groups are preferably exemplified. These (E) components are preferably those having good compatibility with the (D) component. In particular, when the viscosity of the whole system is low, use of a material having low compatibility may cause phase separation and cause poor curing. Specifically showing the structure of such an organohydrogenpolysiloxane, for example,

(In the formula, 2 ≦ b + c ≦ 50, 2 ≦ b, and 0 ≦ c. R may be a hydrocarbon group having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups) ,

(In the formula, 0 ≦ d + e ≦ 50, 0 ≦ d, 0 ≦ e. R may be a hydrocarbon group having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups) Or

(In the formula, 3 ≦ f + g ≦ 20, 2 ≦ f, 0 ≦ g <18. R may be a hydrocarbon group having 2 to 20 carbon atoms in the main chain and containing one or more phenyl groups. And the like, which are chain-like or cyclic, etc.

式中、２≦ｋ、０≦ｌ≦８であり、Ｒは炭素数８以上の炭化水素基である。 Specific examples of the component (E) having compatibility with the component (D) and the component (F), or having relatively good dispersion stability and curing rate include the following.

In the formula, 2 ≦ k, 0 ≦ l ≦ 8, and R is a hydrocarbon group having 8 or more carbon atoms.

但し、２≦ｐ、１≦ｑ≦８である。 As a more specific example of the component (E), methylhydrogenpolysiloxane is used for the purpose of ensuring compatibility with the component (D) and adjusting the amount of SiH, α-olefin, styrene, α-methylstyrene, Examples include compounds modified with allyl alkyl ethers, allyl alkyl esters, allyl phenyl ethers, allyl phenyl esters, and the like, and examples include the following structures.

However, 2 ≦ p and 1 ≦ q ≦ 8.

  In the pressure-sensitive adhesive composition of the present invention, [amount of hydrosilyl group in component (E)] / [amount of alkenyl group in component (D)] is preferably 0.3 to 2.0, preferably 0.4 to More preferably, it is in the range of 1.2. It is not preferable that the amount of [hydrosilyl group in component (E)] / [the amount of alkenyl group in component (D)] exceeds 2.0 because the excess (E) component impairs adhesive properties. . When the [amount of hydrosilyl group in the component (E)] / [amount of alkenyl group in the component (D)] is less than 0.3, the crosslinking becomes too loose, resulting in the occurrence of adhesive residue during re-peeling and high temperatures. This is not preferable because there is a concern that the retention of characteristics may decrease.

  Although the detailed mechanism by which the pressure-sensitive adhesive composition of the present invention can exhibit good pressure-sensitive adhesive properties is unknown, it is effective for the development of pressure-sensitive adhesive properties that the cured product obtained by the present invention has an appropriate crosslinking density. Presumed. Therefore, the average hydrosilyl group content in one molecule of the hydrosilyl group-containing compound which is the component (F) of the present invention is preferably 10 or less, more preferably 5 or less, and 3 or less. More preferably. Moreover, it is preferable that it is 1 or more, and it is more preferable that it is 2 or more.

It does not specifically limit as a hydrosilylation catalyst which is (F) component of this invention, Arbitrary things can be used. For example, solid platinum supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black, etc .; platinum-vinylsiloxane complex {for example, Pt _X (ViMe ₂ SiOSiMe ₂ Vi) _y , Pt [(MeViSiO) ₄ ] _z }; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, x, y and z represent integers), Pt ( acac) ₂ (However, acac represents acetylacetonato), also platinum described in U.S. Pat. No. 3,159,601 and 3,159,662 of Ashby et al - hydrocarbon complex, and Lam Platinum alcoholate catalysts described in reaux et al., U.S. Patent No. 3,220,972 may also be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl _{4 and the} like.

These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable. Although there is no restriction | limiting in particular as a usage-amount of a catalyst, It is good to use in the range of 10 ^<-8 > ^-10 < ^-1 > mol with respect to ¹ mol of alkenyl groups in (D) component. Preferably, it is used in the range of 10 ⁻⁶ to 10 ⁻² mol. If it is less than 10 ⁻⁸ mol, the curing rate is slow and the curability is likely to be unstable. Conversely, when it exceeds 10 ⁻¹ mol, it is difficult to ensure the pot life, which is not preferable.

  In the pressure-sensitive adhesive composition (G) of the present invention, a storage stability improving agent can be used for the purpose of improving storage stability. As the storage stability improver, any conventional stabilizer known as a storage stabilizer of the component (E) of the present invention may be used as long as it achieves the intended purpose, and is particularly limited. is not. Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like can be preferably used. Specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) benzothiazole, 2-methyl-3-butyn-2-ol, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, Examples include 3-methyl-1-butyn-3-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, etc. It is not limited to.

  The pressure-sensitive adhesive composition (G) of the present invention is added with an adhesion-imparting agent for improving the adhesion to various supports (metal core, plastic film, metal foil, paper, etc.) as necessary. be able to. Examples of the adhesion imparting agent include various silane coupling agents and epoxy resins. In particular, a silane coupling agent having a functional group such as an epoxy group, a methacryloyl group, or a vinyl group is easy to use because it has little influence on curability and has a large effect on expression of adhesiveness. However, silane coupling agents that can be used are not limited to these. Moreover, the catalyst for making a silyl group or an epoxy group react can be added together with a silane coupling agent and an epoxy resin. In their use, the impact on the hydrosilylation reaction must be considered.

  In addition, various fillers, antioxidants, ultraviolet absorbers, pigments, surfactants, solvents, and silicon compounds may be appropriately added to the pressure-sensitive adhesive composition (G) of the present invention. Specific examples of the filler include silica fine powder, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate and the like.

  Furthermore, a tackifying resin can be added to the pressure-sensitive adhesive composition (G) of the present invention as necessary in order to improve the properties such as tack. Examples of the tackifying resin include terpene resin, terpene phenol resin, petroleum resin, rosin ester, and the like, and can be freely selected according to the application.

  Further, from the viewpoint of improving the characteristics, it is possible to add resins such as phenol resin, acrylic resin, styrene resin, xylene resin. Moreover, it is possible to add adhesive components, such as an acrylic adhesive, a styrene block adhesive, and an olefin adhesive, for the same purpose.

  The pressure-sensitive adhesive product with a release substrate of the present invention can be used for general office use, medical use, hygiene material use, paper diaper use, PP film bonding, re-peeling use, general packaging use, electrical use and fixing use. It can be used. The pressure-sensitive adhesive product with a release substrate of the present invention is a pressure-sensitive adhesive tape for packaging, an office pressure-sensitive adhesive tape, a coating masking tape, an electrical insulating pressure-sensitive adhesive tape, a binding pressure-sensitive adhesive tape, a protective pressure-sensitive adhesive tape, an identification / decorative pressure-sensitive adhesive tape, and a sheet. , Surgical tape, first-aid bag, percutaneous absorption tape preparation, sports tape, medical adhesive tape, double-sided adhesive tape, electromagnetic interference prevention film and tape, re-peeling film and tape, decorative board film, semiconductor chip transport tape, marking film, Protection film for deep drawing, glass scattering prevention film, foam adhesive tape, waterproof / waterproof tape, anticorrosion adhesive tape, surface protection adhesive tape, dicing adhesive tape, back grinding adhesive tape, printing adhesive sheet, adhesive Can be used for labels, etc.

  In producing the above-mentioned adhesive product, chemicals, electromagnetic wave absorbing materials, light absorbers, foaming components, and the like can be added in accordance with these applications.

  As the base material used for the lower substrate and the upper substrate of the present invention, various known materials can be used without particular limitation, and examples thereof include paper, plastic, and plastic film. Specific examples of the paper include polyethylene laminated paper, glassine paper, clay coated paper, high quality paper, coated paper, thermal paper, and synthetic paper. Examples of the plastic include polyethylene terephthalate, polypropylene, and polyethylene.

  Next, the manufacturing method of the pressure-sensitive adhesive product with a release agent of the present invention will be described with reference to an example of the manufacturing process. However, the manufacturing method of the adhesive product with a release agent of the present invention is not limited to the following examples.

  After applying a composition (C) comprising a cationically polymerizable epoxy group-containing silicone resin (A) and a cationic polymerization initiator (B) on a release substrate, the composition is cured using a known ultraviolet curing system. By forming a silicone release layer, a release substrate with a silicone release layer is produced. The pressure-sensitive adhesive composition (G) of the present invention is applied to the release layer surface of the release substrate with the silicone release layer by a coater, and this is heat-cured to obtain a pressure-sensitive adhesive product. Next, if necessary, the adhesive substrate with a release substrate is obtained by attaching the upper substrate to the adhesive layer.

  As a method of obtaining the pressure-sensitive adhesive product with a release substrate of the present invention, as described above, the pressure-sensitive adhesive composition (G) may be applied to a release substrate with a silicone release layer, and the upper substrate may be bonded together. In addition, after the pressure-sensitive adhesive composition (G) is cured on the upper substrate, any method of laminating a release substrate with a silicone release layer is possible.

  In order to ensure the coatability to the upper substrate or the release substrate with the silicone release layer, it is effective to add additives such as a repellency inhibitor and a release accelerator. As the repellency inhibitor and the releasability accelerator, silicone, acrylic, fluorine, and the like can be used.

  The method for thermosetting the pressure-sensitive adhesive composition (G) of the present invention is not particularly limited, but the temperature varies depending on the type of polymer used and the compound to be added, but is usually within the range of 50 ° C to 180 ° C. Is preferred. The curing time varies depending on the polymer to be used, the compound to be added, the reaction temperature, and the like, but is usually in the range of 0.1 minute to 24 hours, preferably 1 minute to 10 hours, more preferably 1 minute to 1 hour. is there.

  Next, the composition of the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

(Production Example 1)
It was obtained by polymerizing propylene oxide using an oxypropylene polymer glycol having a number average molecular weight of 3,000, which was polymerized using a complex metal cyanide complex catalyst (zinc hexacyanocobaltate) using caustic as a catalyst. Using an oxypropylene polymer and obtaining a number average molecular weight of 28,000 according to the method of Synthesis Example 1 of JP-A-5-117521, a 28% methanol solution of sodium methylate and allyl chloride were used. After converting the terminal to an allyl group, desalting purification was performed to obtain a polyoxyalkylene polymer (D-1) having approximately two allyl terminals in one molecule. The amount of allyl terminal groups of the obtained polyoxyalkylene polymer having an allyl terminal was 0.11 mmol / g.

(Production Example 2)
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene in the total amount of hydrosilyl groups was added to methylhydrogen silicone having an average of five (—Si—O—) repeating units, and an average of 2. A compound (E-1) having 5 hydrosilyl groups was obtained. The Si—H group content of this compound was 5.5 mmol / g.

(Production Example 3)
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total amount of hydrosilyl groups is added to methylhydrogen silicone having an average of 10 (-Si-O-) repeating units, and an average of 5 per molecule. A compound (E-2) having a hydrosilyl group was obtained. The Si—H group content of this compound was 4.2 mmol / g.

(Adhesive composition example 1)
100 parts by weight of the allyl group-terminated polyoxyalkylene polymer (D-1) obtained in Production Example 1 and 0.5 parts by weight of hindered phenol antioxidant (Irganox 1010 manufactured by Ciba Specialty Chemicals), platinum 0.08 parts by weight of vinyl siloxane (3% platinum isopropanol solution), 2 parts by weight of the compound (E-1) having a hydrosilyl group obtained in Production Example 2, and 0.05 parts by weight of dimethyl maleate are mixed to obtain an adhesive composition. (G-1) was obtained.

(Adhesive composition example 2)
100 parts by weight of the allyl group-terminated polyoxyalkylene polymer (D-1) obtained in Production Example 1 and 0.5 parts by weight of hindered phenol antioxidant (Irganox 1010 manufactured by Ciba Specialty Chemicals), platinum 0.08 parts by weight of vinyl siloxane (3% platinum isopropanol solution), 1.2 parts by weight of the compound (E-2) having a hydrosilyl group obtained in Production Example 2, and 0.05 parts by weight of dimethyl maleate were mixed to produce an adhesive. A composition (G-2) was obtained.

Example 1
80 parts by weight of a cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200” and 20 parts by weight of a cationically polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVRCA200”) are stirred and mixed. Then, 3 parts by weight of a cationic polymerization initiator (trade name “Silicolys CATA211”, manufactured by Rhodia) was added and mixed to obtain a release agent composition. It was applied so as to be 4 g / m ² and cured by irradiating ultraviolet rays to obtain a release substrate, and the pressure-sensitive adhesive composition (G-1) was rolled at room temperature on the obtained release substrate. Using a coater, the adhesive layer was coated to a thickness of 50 μm, cured by heating at 130 ° C. for 3 minutes, and a 38 μm thick polyethylene film was formed on the upper surface of the adhesive layer. A phthalate film was bonded and stored at 50 ° C. for 24 hours to obtain an adhesive product with a release substrate.

(Example 2)
80 parts by weight of a cationically polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”) and 20 parts by weight of a cationically polymerizable epoxy group-containing silicone resin (Rhodia, tradename “Silicolys UVRCA200”) are mixed with stirring. Then, 3 parts by weight of a cationic polymerization initiator (trade name “Silicolys CATA211”, manufactured by Rhodia Co., Ltd.) was added and mixed to obtain a release agent composition. The obtained release agent composition was applied to a polyethylene terephthalate film having a thickness of 50 μm so that the coating amount was 0.4 g / m ² and cured by irradiation with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-2) was applied at room temperature using a roll coater so as to have a pressure-sensitive adhesive layer thickness of 50 μm and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Example 3)
To 100 parts by weight of a cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”), 0.5 parts by weight of cationic polymerization initiator (Rhodia, trade name “Silicolys CATA211”) is added and mixed. A release agent composition was obtained. The obtained release agent composition was applied to fine paper so that the coating amount was 0.4 g / m ² and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

Example 4
Add 100 parts by weight of cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”) to 3 parts by weight of cationic polymerization initiator (Rhodia, trade name “Silicolys CATA211”) An agent composition was obtained. The obtained release agent composition was applied to fine paper so that the coating amount was 0.4 g / m ² and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Example 5)
Add 100 parts by weight of cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”) to 3 parts by weight of cationic polymerization initiator (Rhodia, trade name “Silicolys CATA211”) An agent composition was obtained. The obtained release agent composition was applied to fine paper so that the coating amount was 0.4 g / m ² and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-2) was applied at room temperature using a roll coater so as to have a pressure-sensitive adhesive layer thickness of 50 μm and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Example 6)
To 100 parts by weight of a cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”), 7 parts by weight of a cationic polymerization initiator (Rhodia, trade name “Silicolys CATA211”) is added, mixed, and peeled. An agent composition was obtained. The obtained release agent composition was applied to fine paper so that the coating amount was 0.4 g / m ² and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Example 7)
Add 100 parts by weight of cationic polymerizable epoxy group-containing silicone resin (Rhodia, trade name “Silicolys UVPOLY200”) to 3 parts by weight of cationic polymerization initiator (Rhodia, trade name “Silicolys CATA211”) An agent composition was obtained. The obtained release agent composition was applied to fine paper so that the coating amount was 1.0 g / m ² and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Comparative Example 1)
After stirring and mixing 100 parts by weight of an alkenyl group-containing silicone resin (trade name “Silicolyse 11367” manufactured by Rhodia) and 7 parts by weight of a hydrosilyl group-containing silicone resin (tradename “Silicolyse XL97A”), a platinum-based 7 parts by weight of a catalyst for thermosetting silicone resin (trade name “Silicolys CATA12070” manufactured by Rhodia Co., Ltd.) was added and further stirred and mixed to obtain a thermosetting release agent composition. The obtained release agent composition was applied to fine paper so that the coating amount was 0.4 g / m ^2, and then the release agent composition was cured by heating at 140 ° C. for 30 seconds to release the release group. The material was obtained. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Comparative Example 2)
100 parts by weight of a mercapto group-containing silicone resin (GE Toshiba Silicone, trade name “TPR6500J”) and 3 parts by weight of a mercapto group-containing silicone resin curing agent (GE Toshiba Silicone, trade name “UV9380C”) are mixed by stirring. Then, a UV curable release agent composition was obtained. The obtained release agent composition was applied to fine paper and cured by irradiating with ultraviolet rays to obtain a release substrate. On the obtained release substrate, the pressure-sensitive adhesive composition (G-1) was applied at room temperature using a roll coater so that the pressure-sensitive adhesive layer thickness was 50 μm, and heated at 130 ° C. for 3 minutes. After curing, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain a pressure-sensitive adhesive product with a release substrate.

(Reference Example 1)
Using a 50 μm thick polyethylene terephthalate (trade name “Lumirror” manufactured by Toray Industries, Inc.) as a release substrate, the pressure sensitive adhesive composition (G-1) is used at room temperature using a roll coater, and the pressure sensitive adhesive layer has a thickness of 50 μm. The film was cured by heating at 130 ° C. for 3 minutes, a 38 μm thick polyethylene terephthalate film was bonded to the upper surface of the pressure-sensitive adhesive layer, and stored at 50 ° C. for 24 hours to obtain an adhesive product with a release substrate.

  The following tests were performed on the pressure-sensitive adhesive products with release substrates obtained in Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1. The results are shown in Table 1.

(Measurement of peel force)
The pressure-sensitive adhesive product with a release substrate was cut into a strip having a width of 50 mm, a 180 ° peel test was performed at 23 ° C. at a speed of 300 mm / min, and the force required for peeling was measured. Peeling force was obtained by applying a pressure-sensitive adhesive immediately after the release substrate was adjusted, and after removing the release substrate after adjusting the release substrate, and then storing the obtained release substrate at 70 ° C. for 24 hours. It performed about the adhesive product with a peeling base material obtained by coating.

(Residual adhesion rate)
After the release substrate obtained in the above Example was stored at 70 ° C. for 24 hours, a polyester adhesive tape (product name “No. 31B” manufactured by Nitto Denko Corporation) was bonded to the surface of the release agent cured film, and 70 ° C. And stored under a load of 25 g / cm ² for 24 hours. After storage, the adhesive tape was peeled off and attached to a stainless steel plate (JIS C2107) with a 2 kg rubber roller. Subsequently, the adhesive tape was subjected to a 180 ° peel test at a rate of 300 mm / min at 23 ° C., and the force required for the peel was measured. As a blank, the peel force when the adhesive tape was directly pasted on a SUS plate and peeled under the same conditions was measured, and the ratio (%) of the former peel force to the latter peel force was determined as the residual adhesion rate. If there are many uncured parts of the release agent composition, the adhesive force of the adhesive tape will decrease due to the transfer of silicone to the adhesive, and this value will be smaller. Is less preferable than lowering.

比較例１に示されるように熱硬化型シリコーン樹脂を剥離剤に用いた場合は、剥離不良になる。比較例２に示されるようにカチオン重合性エポキシ基含有シリコーンでは無い紫外線硬化型シリコーン樹脂を剥離剤に用いた場合は、粘着剤層の硬化不良のため十分な粘着特性が得られない。参考例１に示されるように、剥離剤層を有しない剥離基材を用いた場合は、粘着力が強すぎて剥離に大きな力を要する。実施例１〜７に示されるように、剥離剤層がカチオン重合性エポキシ基含有シリコーン樹脂(Ａ)及びカチオン重合開始剤（Ｂ）からなる組成物（Ｃ）を紫外線照射して得られる硬化物を剥離基材として使用することで、粘着剤層がアルケニル基を有するポリオキシアルキレン重合体（Ｄ）、ヒドロシリル基を有する化合物（Ｅ）、ヒドロシリル化触媒（Ｆ）を必須成分としてなる粘着剤組成物（Ｇ）に対して優れた剥離性を示すことより、該粘着剤組成物を粘着剤層として持つ粘着製品として使用することができる。

As shown in Comparative Example 1, when a thermosetting silicone resin is used as a release agent, peeling failure occurs. As shown in Comparative Example 2, when an ultraviolet curable silicone resin that is not a cationically polymerizable epoxy group-containing silicone is used as a release agent, sufficient adhesive properties cannot be obtained due to poor curing of the adhesive layer. As shown in Reference Example 1, when a release substrate that does not have a release agent layer is used, the adhesive force is too strong and a large force is required for peeling. As shown in Examples 1 to 7, a cured product obtained by irradiating a composition (C) having a release agent layer comprising a cationic polymerizable epoxy group-containing silicone resin (A) and a cationic polymerization initiator (B) with ultraviolet rays. Is a pressure-sensitive adhesive composition comprising, as an essential component, a polyoxyalkylene polymer (D) having an alkenyl group, a compound (E) having a hydrosilyl group, and a hydrosilylation catalyst (F). By exhibiting excellent peelability to the product (G), it can be used as an adhesive product having the adhesive composition as an adhesive layer.

Claims (11)

A release substrate having a release agent layer and an adhesive product with a release substrate having an adhesive layer formed on the release agent layer side , wherein the release agent layer comprises a cationically polymerizable epoxy group-containing silicone resin (A) and A polyoxyalkylene polymer (D) having a silyl group and a cured product obtained by irradiating a composition (C) comprising a cationic polymerization initiator (B) with ultraviolet rays, and a compound having a hydrosilyl group (E), the cured product der Ru peel group member with adhesive products of the adhesive composition comprising as essential components a hydrosilylation catalyst (F) (G). The pressure-sensitive adhesive product with a peeling substrate according to claim 1, which has a lower substrate, a peeling agent layer, a pressure-sensitive adhesive layer, and an upper substrate used in this order for the peeling substrate. It is an adhesive label with a peeling base material or an adhesive tape with a peeling base material, The adhesive product with a peeling base material of Claim 1 or 2 . The pressure-sensitive adhesive product with a release substrate according to claim 2 or 3, wherein the lower substrate and the upper substrate are at least one selected from paper, polyethylene terephthalate, polypropylene, and polyethylene.   Composition (C) contains a solvent, The adhesive product with a peeling base material in any one of Claims 1-4.   The content (in terms of solid content) of the cationic polymerization initiator (B) in the composition (C) is 0.3 to 0.8 weight based on 100 parts by weight of the solid content of the cationic polymerizable epoxy group-containing silicone resin (A). The pressure-sensitive adhesive product with a release substrate according to claim 1, which is a part.   The pressure-sensitive adhesive product with a release substrate according to any one of claims 1 to 6, wherein the cationic polymerization initiator (B) is an onium salt compound. The release agent layer according to any one of claims 1 to 7, wherein the content of the cationic polymerization initiator (B) is adjusted to 0.8 to 3.5 mg per 1 m ^{2 of the} layer. Adhesive product with release substrate.   The pressure-sensitive adhesive with a release substrate according to any one of claims 2 to 8, wherein [the amount of hydrosilyl groups of the compound (E)] / [total amount of alkenyl groups in the component (D)] is 0.4 to 1.2. Product.   The pressure-sensitive adhesive product with a release substrate according to any one of claims 2 to 9, wherein the polyoxyalkylene polymer having an alkenyl group (D) has a molecular weight of 6,000 to 50,000.   The pressure-sensitive adhesive product with a release substrate according to any one of claims 2 to 10, wherein (E) is a compound having an average of 1 to 5 hydrosilyl groups in one molecule.