KR20070031374A - Silicone Pressure Sensitive Adhesive and Adhesive Tape - Google Patents

Abstract

Crude rubber containing an average of more than one alkenyl group per molecule of organopolysiloxane (a) and essentially of R _{¹ 3} SiO _^1/2 units and SiO _4/2 units organosilane mixture or partial condensation of the organopolysiloxane resin (b) consisting of Product (A), organopolysiloxane (B) comprising an average of at least two silicon-bonded hydrogen atoms per molecule, phenolic oxidation inhibitors and / or phenol-modified organosiloxanes (C), aromatic amino type oxidation inhibitors, and Silicone-based pressure sensitive adhesives comprising aromatic amino-modified organosiloxanes (D) and platinum-based catalysts (E) may form pressure sensitive adhesive layers that maintain good removal after exposure to high temperatures.

Organopolysiloxane, phenol-type oxidation inhibitor, amino-type oxidation inhibitor, platinum catalyst, silicone pressure-sensitive adhesive, removal ability.

Description

Silicone pressure sensitive adhesive and adhesive tape {Silicone-based pressure-sensitive adhesive and adhesive tape}

The present invention relates to a silicone-based sensitizing adhesive and an adhesive tape produced using such an adhesive. More specifically, the present invention relates to silicone-based pressure sensitive adhesives capable of forming a pressure sensitive adhesive layer of good removal after exposure to high temperatures. The present invention also relates to adhesive tapes that maintain good removal after exposure to high temperatures.

Silicone-based pressure sensitive adhesives are characterized by good electrical insulation properties, heat resistance, adhesive strength and other useful properties, so they find wide application in situations where certainty is required.

In particular, in order to improve the heat resistance of silicone pressure-sensitive adhesives, these compounds may be selected from cerium-containing compounds (see Japanese Patent Application Laid-open No. Hei 6-96698), and materials containing organosilicon compounds containing BO-Si bonds. Reference: Japanese Patent Laid-Open No. 7-11228] or a phenolic oxidation inhibitor (corresponding to Japanese Patent Laid-Open No. 2003-96429, corresponding to US Pat. No. 6,815,076) has been proposed.

However, the use of an adhesive tape utilizing a silicon-based pressure-sensitive adhesive with a material containing a cerium-containing compound or an organosilicon compound containing a B-O-Si bond is problematic. This problem is that after the adhesive tape has been exposed to high temperatures, it is peeled off from its substrate, leaving part of the pressure-sensitive adhesive layer on the substrate. In comparison to adhesives of the type mentioned above, adhesives comprising phenolic oxidation inhibitors are less subject to this problem, but they still leave part of the pressure-sensitive adhesive layer when exposed to high temperatures over long periods of time. Therefore, when an adhesive tape based on the use of the above-mentioned pressure-sensitive adhesive is used as a masking tape, for example, in a solder reflux process on a printed-circuit substrate, the heat treated substrate after removal of the tape The pressure-sensitive adhesive layer remaining on the surface of the causes problems for subsequent processing of the product.

It is an object of the present invention to provide a silicone-based pressure sensitive adhesive capable of forming a pressure sensitive adhesive layer that maintains good removal capacity after exposure to high temperatures. It is another object to provide an adhesive tape that maintains good removal after exposure to high temperatures.

Summary of the Invention

Silicone pressure sensitive adhesive of the present invention,

Essentially as crude rubber-based organo polysiloxane acid (a) containing an average of more than one alkenyl group per molecule, R _{¹ 3} SiO _^1/2 unit [where, R ¹ is optionally substituted with a monovalent hydrocarbon group; and SiO _4/2 is made of a unit, SiO _4/2 units R _{¹ 3} SiO _^1/2 unit molar ratio is 0.5 to 1.5 of the organosilane mixture of organopolysiloxane resin (b) or part of the condensation product of (a),

Organopolysiloxane (B) comprising an average of at least two silicon-bonded hydrogen atoms per molecule, wherein the silicon-bonded hydrogen atoms of the component are from 0.5 to 150.0 moles per molecule of the alkenyl group of component (A) Exists],

Phenolic oxidation inhibitor and / or phenol-modified organosiloxane (C) in an amount of 0.001 to 10 parts by weight, based on 100 parts by weight of components (A) and (B),

0.001 to 10 parts by weight of the aromatic amino type oxidation inhibitor and / or the aromatic amino-modified organosiloxane (D) per 100 parts by weight of the component (A) and the component (B) and

The platinum-based catalyst (E) is included in an amount sufficient to cure the adhesive.

The adhesive tape of the present invention comprises a film substrate and a silicone pressure sensitive adhesive layer formed on the film substrate by curing the above-mentioned silicone pressure sensitive adhesive on the film substrate.

Effects of the Invention

The silicone pressure sensitive adhesives of the present invention are suitable for forming pressure sensitive adhesive layers that maintain good removal after exposure to high temperatures. The adhesive tapes of the present invention also have properties of good removal after exposure to high temperatures.

The following is a more detailed description of the silicone pressure-sensitive adhesive of the present invention.

Crude rubber organopolysiloxane (a) and essentially of R _{¹ 3} SiO _^1/2 units of component (A) is one of the main components of the composition comprising the alkenyl group one or more of the average in each molecule [wherein, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group; and SiO _4/2 is made of a unit, a mixture of R _{¹ 3} SiO _^1/2 in the organopolysiloxane resin (b) units molar ratio of 0.5 to 1.5 of the SiO _4/2 units to be. Component (A) may also comprise partial condensation products of the abovementioned components.

The crude rubber-based organopolysiloxane of component (a) contains an average of at least one alkenyl group per molecule. If the average number of alkenyl groups contained in one molecule of component (a) is less than 1, the pressure sensitive adhesive obtained will have a low cohesive strength (holding capacity). When component (a) is a crude rubber system, it is recommended that its plasticity be 50 to 200, preferably 80 to 180 (plasticity is 4.2 g using 1 kgf force at 25 ° C. for 3 minutes according to JIS K 6249). Measured on spherical samples). There is no specific limitation on the molecular structure of component (a), but linear or partially branched linear molecular structure is preferred. The alkenyl groups of component (a) can be, for example, vinyl, allyl, butenyl or pentenyl groups, with vinyl groups being preferred. Silicon-bonded groups other than the alkenyl groups of component (a) may be, for example, methyl, ethyl, propyl, butyl, pentyl, heptyl or similar alkyl groups; Phenyl, tolyl, xylyl or similar aryl groups; Benzyl, phenethyl or similar aralkyl groups; Chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups or other monovalent hydrocarbons; Hydroxyl groups, methoxy, ethoxy, propoxy or similar alkoxy groups; Acetoxy group; Isopropenoxy group; It may be an aminooxy group or similar hydrolyzable group. Most preferred among these are methyl and phenyl groups. When component (a) is subjected to partial condensation with component (b) described below, component (a) must contain at least 0.01% by weight of silicon-bonded hydroxyl groups or silicon-bonded hydrolyzable groups.

Component (b) is an organopolysiloxane resin consisting essentially of a R _{¹ 3} SiO _^1/2 units and SiO _4/2 units. In the above formula, R ¹ is methyl, ethyl, propyl, butyl, pentyl, heptyl or similar alkyl group; Vinyl, allyl, butenyl, pentenyl or similar alkenyl groups; Phenyl, tolyl, xylyl or similar aryl groups; Benzyl, phenethyl or similar aralkyl groups; Substituted or unsubstituted monovalent hydrocarbon groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups, or another substituted or unsubstituted monovalent hydrocarbon group. When component (b) is subjected to the partial condensation reaction with component (a) mentioned above, component (b) must contain at least 0.01% by weight of silicon-bonded hydroxyl groups or silicon-bonded hydrolyzable groups. Hydrolyzable groups include methoxy, ethoxy, propoxy or similar alkoxy groups; Acetoxy group; Isopropenoxy group; And an aminooxy group. Component (b) it is essentially composed of R _{¹ 3} SiO _^1/2 units and SiO _4/2 units. It may also contain a R ¹ ₂ SiO _2/2 units and R ¹ SiO _3/2 units. The R ¹ ₃ SiO _3/2 the total amount of units and SiO _4/2 units in the component (b) is recommended that the 50 weight%, preferably 80 weight%, even more preferably from 100% by weight, that is, It is preferred that component (b) consists of only the two types of units mentioned above. The molar ratio of R ¹ ₃ SiO _3/2 units to SiO _4/2 units is to be 0.5 to 1.5, preferably from 0.5 to 1.0, further more preferably from 0.6 to 0.9. If the molar ratio mentioned above is below the recommended lower limit, the pressure sensitive adhesive obtained will have a low adhesive strength. On the other hand, if the ratio exceeds the recommended upper limit, this will reduce the cohesive strength of the pressure-sensitive adhesive obtained.

Component (A) may comprise a mixture of components (a) and (b) or no production of partial condensation thereof. In component (A), component (a) and component (b) are in a weight ratio of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, even more preferably 3: 7 to 7: 3. Should be used. Partial condensation can be carried out in various ways, for example with heating or with a catalyst such as potassium hydroxide, barium hydroxide or similar systems, ammonia water; Methylamine, ethylamine, propylamine or similar amines; Tetrabutyl titanate, tetraisobutyl titanate or similar titanium compounds; Octyl tin diacetate or similar tin compound; It may be carried out by partial condensation in the presence of hexamethyldisilazane and the like.

Component (B) is the crosslinker of the composition. This includes organopolysiloxanes containing on average two or more silicon-bonded hydrogen atoms per molecule. The binding site for silicon may be at the molecular terminal and / or side chain. Groups other than hydrogen atoms capable of bonding to silicon include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or similar alkyl groups; Phenyl, tolyl, xylyl, naphthyl or similar aryl groups; Benzyl, phenethyl or similar aralkyl groups; Chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups and other substituted or unsubstituted monovalent hydrocarbon groups except alkenyl groups. Most preferred methyl and phenyl groups. Component (B) may have a linear, branched, cyclic, reticulated or partially branched linear molecular structure. Linear molecular structures are preferred. There is no specific limitation regarding the viscosity of component (B) at 25 ° C., but it is recommended to have a viscosity of 0.1 to 500,000 mPa · s, preferably 1 to 100,000 mPa · s.

Organopolysiloxanes of component (B) can be exemplified by the following compounds: methylhydrogenpolysiloxanes terminated at both ends of the molecule with trimethylsiloxy groups, methylhydrogensiloxanes terminated at both ends of the molecule with trimethylsiloxy groups Copolymer of dimethylsiloxane with methylphenylsiloxane terminated with trimethylsiloxy groups at both ends of the molecule, copolymer of methylhydrogensiloxane and dimethylsiloxane, dimethylpolysiloxane terminated with dimethylhydrogensiloxy groups at both ends of the molecule both ends of a dimethyl hydrogen siloxy group, a terminal treatment of methylphenylsiloxane and dimethylsiloxane copolymer, the molecular both ends of a dimethyl hydrogen siloxy group, the terminal processing the methylphenyl polysiloxane, a siloxane unit of formula R _{² 3} SiO ^_1/2 of the formula R ^{₂ 2} HSiO ^_1/2 siloxane units and O consisting of siloxane units of the formula SiO _4/2 Organopolysiloxane resin, the formula R ^{₂ 2} HSiO ^_1/2 siloxane units and formula SiO _4/2 organopolysiloxane resin composed of siloxane units, R ^₂ HSiO _^2/2 siloxane units, and the general formula R _² SiO ^_3/2) or ( HSiO _3/2 consisting of a siloxane unit of organopolysiloxane resin or the above-mentioned two of the organo polysiloxane or more mixture. In the above formula, R ² may be a substituted or unsubstituted same monovalent hydrocarbon group as defined above except for an alkenyl group.

Component (B) is 0.5 to 150 water per mole of the total alkenyl groups of component (A), preferably 0.6 to 150.0 moles, more preferably 0.7 to 140.0 moles, more preferably the silicon-bonded hydrogen atoms present in the component More preferably from 0.8 to 130.0 moles. When component (B) is used in an amount below the recommended lower limit, it is difficult to provide complete curing of the pressure-sensitive adhesive obtained or the adhesive obtained may have insufficient cohesive strength (holding capacity). On the other hand, if component (B) is used in an amount exceeding the recommended upper limit, this will increase the resistance to peeling from the paper or film substrate. In addition, the resistance to exfoliation mentioned above will increase over time.

Component (C) is used to improve the removal capacity after exposure to high temperatures. Such components include phenolic oxidation inhibitors and / or phenol-modified organosiloxanes. Phenolic antioxidants may include monophenolic antioxidants, nonphenolic antioxidants, polyphenolic antioxidants or hindered phenol oxidation inhibitors, with hindered phenol oxidation inhibitors being preferred. The following are specific examples of phenolic oxidation inhibitors of component (C): 2,6-di-tert-butyl-p-cresol, 2,4,6-tri-tert-butylphenol, n-octyl-3 -(4'-hydroxy-3 ', 5'-di-tert-butylphenol) propionate, n-octadecyl-3- (4'-hydroxy-3', 5'-di-tertiary -Butylphenol) propionate, styrenated phenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,5-di-tert-butyl-hydroquinone, cyclohexylphenol, butyl hydride Roxyanisole, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4, 4'-i-propylidene bisphenol, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 4,4'-methylene-bis (2,6-di-tert-butylphenol), 2,6 -Bis (2'-hydroxy-3'-tert-butyl-5'methylbenzyl) -4-methylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tertiary- Butylphenyl) butane, 1,3,5-tris'methyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- ( 3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4-hydroxy-3,5-di-tert-butylphenyl trimethoxysilane, 4-hydroxy-3,5-di -Tert-butylphenyl triethoxysilane, 4-hydroxy-3,5-di-tert-butylphenyl methyldimethoxysilane, 3- (4-hydroxy-3,5-di-tert-butyl Phenyl) propyltrimethoxysilane, 3- (4-hydroxy-3,5-di-tert-butylphenyl) propylmethyldimethoxysilane and 3- (4-hydroxy-3,5-di-tertiary -Butylphenyloxy) propyltrimethoxysilane.

의 하이드록시페닐 함유 그룹 또는 화학식

의 하이드록시페닐 함유 그룹이되, 분자 내의 하나 이상의 R³은 위에서 언급한 하이드록시페닐 함유 그룹 중의 임의의 것에 의해 나타낼 수 있다]으로 나타낸다There is no particular limitation with regard to the phenol-modified oxanosiloxane of component (C), but this presupposes having one or more hydroxyphenyl containing groups bonded to silicon atoms per molecule. There is no particular limitation on the bonding position of the hydroxyphenyl containing group. For example, it may bind to the molecular terminus and / or the molecular side chain. There is no limitation as to the molecular structure of the organosiloxane which may have a linear, cyclic, branched or partially branched linear molecular structure. Linear structures are preferred. The phenol-modified organosiloxanes mentioned above are for example average formulas of R ³ _a SiO _{(4-a) / 2} , wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group, formula

Of hydroxyphenyl-containing groups or formulas

Wherein at least one R ³ in the molecule can be represented by any of the aforementioned hydroxyphenyl containing groups.

The following are substituted and unsubstituted monovalent hydrocarbon groups represented by R ³ : methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or similar alkyl groups; Vinyl, allyl, butenyl, pentenyl or similar alkenyl groups; Phenyl, tolyl, naphthyl or similar aryl groups; Benzyl, phenethyl or similar aralkyl groups; Chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups.

또는 화학식

[여기서, R⁴ 및 R⁵는 탄소수 1 내지 10의 동일하거나 상이한 선형 또는 분지형 알킬 그룹이다]으로 나타낼 수 있다. 상기 선형 알킬 그룹은 메틸, 에틸, 프로필, 부틸, 펜틸, 헥실 및 헵틸 그룹으로 예시될 수 있다. 위에서 언급한 분지형 알킬 그룹은 이소프로필, 3급-부틸 및 3급-펜틸 그룹으로 예시될 수 있다. 위의 화학식에서, X는 단일 결합, 옥시 그룹, 알킬렌 그룹, 옥시알킬렌 그룹 또는 알킬렌카보닐 옥시알킬렌 그룹을 나타낸다. 알킬렌 그룹은 메틸렌, 에틸렌 및 프로필렌 그룹으로 나타낼 수 있다. 옥시알킬렌 그룹은 옥시에틸렌 및 옥시프로필렌 그룹으로 나타낼 수 있고, 위에서 언급한 알킬렌카보닐 옥시알킬렌 그룹은 에틸렌카보닐 옥시프로필렌 그룹 및 프로필렌카보닐 옥시프로필렌 그룹으로 나타낼 수 있다. 위의 화학식에서, "a"는 1.5 내지 3.0, 바람직하게는 1.8 내지 3.0이다.In addition, the hydroxyphenyl containing group represented by R ³ is also represented by the formula

Or chemical formula

Wherein R ⁴ and R ⁵ are the same or different linear or branched alkyl groups having 1 to 10 carbon atoms. Such linear alkyl groups can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups. The branched alkyl groups mentioned above can be exemplified by isopropyl, tert-butyl and tert-pentyl groups. In the above formula, X represents a single bond, oxy group, alkylene group, oxyalkylene group or alkylenecarbonyl oxyalkylene group. Alkylene groups can be represented by methylene, ethylene and propylene groups. The oxyalkylene group may be represented by an oxyethylene and oxypropylene group, and the above-mentioned alkylenecarbonyl oxyalkylene group may be represented by an ethylenecarbonyl oxypropylene group and a propylenecarbonyl oxypropylene group. In the above formula, "a" is 1.5 to 3.0, preferably 1.8 to 3.0.

The above-mentioned phenol-modified oxanosiloxane is disclosed, for example, in JP-A-61-43692 and JP-A-2-261823, and can be represented by the following specific compounds. In the following formulae, "m" and "n" are positive numbers.

Component (C) should be used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 8 parts by weight, even more preferably 0.01 to 5 parts by weight, per 100 parts by weight of component (A) and component (B). If component (C) is added in an amount below the recommended lower limit, this may impair the removal capacity after exposure to high temperatures. On the other hand, if component (C) is added in an amount exceeding the recommended upper limit, this will cause incomplete curing or reduce the cohesive strength and bonding of the composition.

In combination with component (C), component (D) also improves removal after exposure to high temperatures. Component (D) may comprise aromatic amino type oxidation inhibitors and / or aromatic amino-modified oxanosiloxanes. Aromatic amino type oxidation inhibitors include phenyl-α-naphthylamine, phenyl-β-naphthylamine or similar naphthylamine type oxidation inhibitors; 4,4 '-(α, α-dimethylbenzyl) diphenylamine, 4,4'-dioctyl-diphenylamine, high temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and acetone, di Low temperature reaction products of phenylamine, aniline and acetone, reaction products of diphenylamine and diisobutylene, octylated diphenylamine, substituted diphenylamines, alkylated diphenylamines, diphenylamine derivatives or other diphenylamine types Oxidation inhibitors; N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N- Phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis ( 1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p -Phenylenediamine, mixture of diallyl-p-phenylenediamine, phenyl-octyl-p-phenylenediamine or similar p-phenylenediamine type oxidation inhibitors; A mixture of phenyl-α-naphthylamine and diphenyl-p-phenylenediamine and amines such as N-isopropyl-N'-phenyl-p-phenylenediamine and 6-ethoxy-2,2,4-trimethyl Illustrated as a mixture of 1,2-dihydroquinoline.

의 방향족 아미노 함유 그룹 및 화학식

의 방향족 아미노 함유 그룹이되, 하나의 분자의 하나 이상의 R⁶은 위에서 언급한 방향족 아미노 함유 그룹 중의 임의의 것을 나타낼 수 있다]로 나타낼 수 있다.There is no particular limitation with regard to the aromatic amino-modified organosiloxane of component (D), but this presupposes having one or more bound aromatic amino containing groups per molecule. There is no restriction as to the bonding position of the aromatic amino containing group. For example, it may bind to the molecular terminus and / or the molecular side chain. There is no limitation as to the molecular structure of the organosiloxane which may have a linear, cyclic, branched or partially branched linear molecular structure. Linear structures are preferred. The aromatic amino-modified organosiloxanes mentioned above are, for example, formula R ⁶ _b SiO _{(4-b) / 2} , wherein R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group, formula

Aromatic amino-containing groups and formulas of

, Wherein at least one R ⁶ of one molecule may represent any of the aromatic amino containing groups mentioned above.

또는 화학식

으로 예시될 수 있다.Substituted indicated by R ⁶ or is unsubstituted 1 may represent the same hydrocarbon groups as referred to above is a hydrocarbon group, wherein the group containing aromatic amino of R ⁶ of the formula

Or chemical formula

It can be illustrated as.

In the above formula, Y is a single bond, oxy group, alkylene group or oxyalkylene group, wherein the alkoxyalkylene group can be represented by methylene, ethylene and propylene. Oxyalkylene groups can be represented by oxymethylene, oxyethylene and oxypropylene groups. In the above formula, "c" is 1 or 2, and "b" is 1.5 to 3.0, preferably 1.8 to 3.0.

The aromatic amino modified organosiloxane mentioned above is disclosed, for example in Unexamined-Japanese-Patent No. 2-283765, and a compound of the following formula (where "m" and "n" are positive numbers). Can be illustrated as:

.

.

In the adhesive composition, component (D) is present in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 8 parts by weight, and even more preferably 0.01 to 5 parts by weight per 100 parts by weight of the total of component (A) and component (B). Should be used. If component (D) is added in an amount below the recommended lower limit, this may impair the removal capacity after exposure to high temperatures. On the other hand, if component (D) is added in an amount exceeding the recommended upper limit, this may cause incomplete curing or reduce the cohesive strength and bonding of the composition.

Component (E) is a platinum catalyst that accelerates crosslinking of the composition. Component (E) can be exemplified by chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum-carbonyl complexes, platinum-alkenylsiloxane complexes and platinum-olefin complexes. The platinum-alkenylsiloxane complex is preferably preferred in view of excellent miscibility with component (A). Platinum-alkenylsiloxane complexes may be exemplified by 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,1,3,3-tetravinyl-1,3-dimethyldisiloxane .

Component (E) should be used in an amount sufficient to accelerate curing of the composition. For example, by weight, it may be used in an amount such that the content of the metal platinum in component (E) accounts for 0.1 to 1,000 ppm, preferably 1 to 500 ppm, per component (A). If component (E) is added in an amount below the recommended lower limit, this will delay the curing of the photosensitive adhesive obtained. On the other hand, if the added content of component (E) exceeds the recommended upper limit, this causes discoloration of the pressure-sensitive adhesive obtained.

The adhesive of the present invention consists of components (A) to (E), but if necessary to control the rate of cure, the composition is 2-methyl-3-butyl-2-ol, 3,5-dimethyl-1- Hexin-3-ol, 3-methyl-1-penten-3-ol, 2-phenyl-3-butyn-2-ol or similar alkyne alcohol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne or similar enine compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenyl-cyclo In combination with curing reaction modifiers such as tetrasiloxane or similar alkenylsiloxane compounds.

The curing reaction modifier mentioned above should be added in an amount sufficient and effective to control the curing rate of the adhesive composition. Generally, the amount added does not exceed 5 parts by weight per 100 parts by weight of component (A). If the added amount exceeds 5 parts by weight, this will delay the curing rate.

If necessary, the adhesive composition may be selected from toluene, xylene, hexene, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone or similar organic solvents; Tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, allyl Various antioxidants, pigments, stable as well as other additives such as trimethoxysilane, allyltriethoxysilane, 3-glycidoxypropylthitrimethoxysilane, 3-methacryloxypropyltrimethoxysilane or similar alkoxysilane compounds It can be combined with a topic.

The silicone pressure-sensitive adhesive of the present invention is prepared by mixing the above-mentioned components (A) to (E), if necessary, any other components. After the obtained additive is applied onto the substrate, it is cured by forming a pressure-sensitive adhesive layer on the surface of the substrate at room temperature or by heating. Adhesives include gravure coatings, offset coatings, offset gravure, roll coatings, reverse-roll coatings, air-knife coatings, curtain coatings, comma coatings, etc. Can be applied.

The following is a more detailed description of the adhesive type of the present invention.

Adhesive types of the present invention include a film substrate and a silicone-based pressure sensitive adhesive formed by curing the above-mentioned pressure sensitive adhesive on the surface of the film substrate. The film base material is polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, nylon, polyether-ether ketone, polyphenylene sulfide, liquid crystal polyarylate, polyether sulfone, polyether imide, etc. It may be a stretched or unstretched plastic film substrate made from the same resin. The film substrate may also consist of film-based plastics coated with the resins mentioned above. When it is necessary to provide heat resistance, polyimide (PI), polyether-ether ketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylene, polyamidoimide (PAI), polyether sulfin (PES), etc. It is recommended to form the film substrate from the.

The adhesive type of the present invention is prepared by applying the above-mentioned silicone-based pressure-sensitive adhesive on the surface of the film substrate and curing the adhesive at room temperature or with heating to form a pressure-sensitive adhesive layer on the surface of the film substrate. The adhesive can be applied in the same way as mentioned above. It is preferable to cure by heat. The heating should be carried out at a temperature above 50 ° C., preferably at a temperature of 80 to 200 ° C.

Example

The pressure sensitive adhesive and adhesive tape of the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples, viscosity values were measured at 25 ° C. and rubber plasticity was measured according to JIS K 6249 (using 1 kgf for 3 minutes at 25 ° C. for 4.2 g spherical samples). Cohesive strength and removal capacity after exposure to high temperatures were measured by the method described below.

[Adhesive strength]

A 40 μm-thick pressure sensitive adhesive layer was formed by curing a silicone pressure sensitive adhesive on the surface of a 25 μm-thick substrate made of polyimide resin, and an adhesive sheet was prepared by heating the product at 120 ° C. for 3 minutes. did. The obtained adhesive sheet is cut into 25 mm-width strings to form an adhesive tape. Using a rubber roller at a pressure of 2 kgf, the adhesive tape was adhered to the pre-polished stainless steel sheet (SUS304) using # 360 wet-treated abrasive paper. The article was kept for 30 minutes at room temperature and the cohesive strength of the adhesive was measured by 180 ° peel-strength experiments using a tension tester operating at a constant drawing speed of 300 mm / min.

[Removability after exposure to high temperature]

An adhesive sheet is prepared by curing a silicone pressure sensitive adhesive on a polyimide-resin substrate and subsequently forming a layer of pressure sensitive adhesive of about 40 μm-thick obtained after heating the coated substrate at 120 ° C. for 3 minutes. The obtained adhesive sheet is cut into 25 mm-width strings to form an adhesive tape. By using a rubber roller at a pressure of 2 kgf, the adhesive tape was adhered to the pre-polished stainless steel sheet (SUS304) using the # 360 wet-treated abrasive paper. The product was heated in an oven for 2 hours at a temperature of 200 to 300 ° C. in increments of 10 ° C. (ie, 200 ° C., 210 ° C., 220 ° C ......), subjected to ageing, and recovered in the oven. The removal capacity was measured by a 180 ° peel-strength test method using a tension tester operated at a constant drawing speed of 300 mm / min. This property was determined by visually observing the transfer of adhesive to the surface of the stainless steel sheet by the following measurement criteria: O—excellent removal of the pressure-adhesive layer without residual adhesive remaining on the stainless steel sheet surface; X-Unsatisfactory removal with residual adhesive remaining on the stainless steel plate surface

Example 1

의 장애 페놀 산화 억제제 [n-옥틸-3-(4'-하이드록시-3',5'-디-3급-부틸페닐)프로피오네이트] 0.15중량부; 화학식

의 디페닐아민형 산화 억제제[여기서, R은 H와 3급-C₈H₁₇의 혼합물이다] 0.15중량부; 및 톨루엔 70.3중량부. 수득한 혼합물을 백금과 1,3-디비닐-1,1,3,3-테트라메틸디실록산의 착물과 (착물 속 금속 백금의 함량을 중량 단위로 메틸폴리실록산 수지와 위에서 언급한 메틸비닐실록산과 디메틸실록산의 경화되지 않은 공중합체의 총량당 100ppm이 되도록) 추가로 결합시켰다. 결과적으로, 오가노폴리실록산 성분 40중량%를 포함하는 실리콘계 감압성 접착제를 제조했다. 접착 테이프는 수득한 실리콘계 감압성 접착제를 사용하여 제조했다. 수득한 접착 테이프는 응집 강도 및 제거능에 대해 실험했다. 결과는 표 1에 나타난다.The mixture was prepared from the following components: 25.6 parts by weight of a crude rubber-based copolymer of methylvinylsiloxane and dimethylsiloxane having both ends of the molecule terminated with dimethylvinylsiloxy groups and having a vinyl group in part of the side chain (plastic 135, vinyl Group content 0.04% by weight); For SiO _4/2 units (CH ₃₎ a ₃ SiO _1/2 molar ratio of 0.8 of the (CH ₃₎ 60% by weight of a methylpolysiloxane resin consisting of ₃ SiO _1/2 units and SiO _4/2 units xylene - 54.6 parts by weight of the diluted solution; 0.2 parts by weight of methylhydrogenpolysiloxane having both ends of the molecule terminated with trimethylsiloxy group and having a viscosity of 20 mPa · s (content of 1.55% by weight of silicon-bonded hydrogen atoms); 0.1 part by weight of 2-methyl-3-butyn-2-ol; Chemical formula

0.15 parts by weight of a hindered phenol oxidation inhibitor [n-octyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate]; Chemical formula

0.15 parts by weight of a diphenylamine type oxidation inhibitor, wherein R is a mixture of H and tert-C ₈ H ₁₇ ; And 70.3 parts by weight of toluene. The resulting mixture was prepared with a complex of platinum, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methyl methyl siloxane resin and the above-mentioned methyl vinyl siloxane, To 100 ppm per total amount of uncured copolymer of dimethylsiloxane). As a result, a silicone pressure sensitive adhesive comprising 40% by weight of an organopolysiloxane component was prepared. An adhesive tape was produced using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The results are shown in Table 1.

Comparative Example 1

The silicone pressure sensitive adhesive was produced in the same manner as in Example 1 except that 0.30 part of the diphenylamine type oxidation inhibitor was used in place of the hindered phenol oxidation inhibitor. An adhesive tape was produced using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The results are shown in Table 1.

Comparative Example 2

The silicone pressure sensitive adhesive was produced in the same manner as in Example 1 except that 0.30 part of the hindered phenol type oxidation inhibitor was used in place of the diphenylamine type oxidation inhibitor. The adhesive tape was produced by using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The results are shown in Table 1.

Example 1 Comparative Example 1 Comparative Example 2 Cohesive Strength (N / m) 264 272 266 Removability (Temperature) 200 ℃ O O O 210 ℃ O O O 220 ℃ O O O 230 ℃ O O O 240 ℃ O O O 250 ℃ O O O 260 ℃ O X X 270 ℃ O X X 280 ℃ O X X 290 ℃ X X X

Example 2

의 페놀-개질된 디메틸실록산 0.15중량부; 화학식

의 방향족 아미노-개질된 디메틸실록산 0.15중량부; 및 톨루엔 70.3중량부. 수득한 혼합물을 백금과 1,3-디비닐-1,1,3,3-테트라메틸디실록산의 착물과 (착물 속 금속 백금의 함량을 중량 단위로 메틸폴리실록산 수지와 위에서 언급한 메틸비닐실록산과 디메틸실록산의 경화되지 않은 공중합체의 총량당 100ppm이 되도록) 추가로 결합시켰다. 결과적으로, 오가노폴리실록산 성분 40중량%를 포함하는 실리콘계 감압성 접착제를 제조했다. 접착 테이프는 수득한 실리콘계 감압성 접착제를 사용하여 제조했다. 수득한 접착 테이프는 응집 강도 및 제거능에 대해 실험했다. 경과는 표 2에 나타난다.The mixture was prepared from the following components: 25.6 parts by weight of a crude rubber-based copolymer of methylvinylsiloxane and dimethylsiloxane having both ends of the molecule terminated with dimethylvinylsiloxy groups and having vinyl groups in part of the side chain (plastic 136, vinyl Group content 0.04% by weight); For SiO _4/2 units (CH ₃₎ a ₃ SiO _1/2 molar ratio of 0.8 of the (CH ₃₎ 60% by weight of a methylpolysiloxane resin consisting of ₃ SiO _1/2 units and SiO _4/2 units xylene - 54.6 parts by weight of the diluted solution; 0.2 parts by weight of methylhydrogenpolysiloxane having both ends of the molecule terminated with trimethylsiloxy group and having a viscosity of 20 mPa · s (content of 1.55% by weight of silicon-bonded hydrogen atoms); 0.1 part by weight of 2-methyl-3-butyn-2-ol; Chemical formula

0.15 parts by weight of a phenol-modified dimethylsiloxane; Chemical formula

0.15 parts by weight of an aromatic amino-modified dimethylsiloxane of; And 70.3 parts by weight of toluene. The resulting mixture was prepared with a complex of platinum, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methyl methyl siloxane resin and the above-mentioned methyl vinyl siloxane, To 100 ppm per total amount of uncured copolymer of dimethylsiloxane). As a result, a silicone pressure sensitive adhesive comprising 40% by weight of an organopolysiloxane component was prepared. An adhesive tape was produced using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The progress is shown in Table 2.

Comparative Example 3

Silicone pressure sensitive adhesives were prepared in the same manner as in Example 2, except that 0.30 part of the aromatic amino-modified dimethylsiloxane was used in place of the phenol-modified dimethylsiloxane. An adhesive tape was produced using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The results are shown in Table 2.

[Comparative Example 4]

Silicone pressure-sensitive adhesives were prepared in the same manner as in Example 2, except that 0.30 part of phenol-modified dimethylsiloxane was used instead of aromatic amino-modified dimethylsiloxane. The adhesive tape was produced by using the obtained silicone pressure sensitive adhesive. The obtained adhesive tape was tested for cohesive strength and removal ability. The results are shown in Table 2.

Example 2 Comparative Example 3 Comparative Example 4 Cohesive Strength (N / m) 274 276 268 Removability (Temperature) 200 ℃ O O O 210 ℃ O O O 220 ℃ O O O 230 ℃ O O O 240 ℃ O O O 250 ℃ O O O 260 ℃ O X X 270 ℃ O X X 280 ℃ O X X 290 ℃ X X X

The silicone pressure sensitive adhesives of the present invention are suitable for forming pressure sensitive adhesive layers of adhesive tapes which are characterized by good removal after exposure to high temperatures. Due to the good removal ability after exposure to high temperatures, the adhesive tapes of the present invention can be used as masking tapes for heat treatment in solder reflux processes on printed circuit boards.

Claims (6)

Essentially as crude rubber organopolysiloxane (a) containing alkenyl groups mean one or more per molecule, R _{¹ 3} SiO _^1/2 unit [where, R ¹ is optionally substituted with a monovalent hydrocarbon group; and SiO _{4 /} is made of a _second unit SiO _{4/2 units,} R _{¹ 3} SiO _^1/2 unit molar ratio is 0.5 to 1.5, the organopolysiloxane resin (b) with a mixture or partial condensation product of the (a), Organopolysiloxane (B) comprising an average of at least two silicon-bonded hydrogen atoms per molecule, wherein the silicon-bonded hydrogen atoms of the component are from 0.5 to 150.0 moles per molecule of the alkenyl group of component (A) Exists in quantities], Phenolic oxidation inhibitor and / or phenol-modified organosiloxane (C) in an amount of 0.001 to 10 parts by weight, based on 100 parts by weight of components (A) and (B), 0.001 to 10 parts by weight of the aromatic amino type oxidation inhibitor and / or the aromatic amino-modified organosiloxane (D) per 100 parts by weight of the component (A) and the component (B) and A silicone pressure sensitive adhesive comprising a platinum catalyst (E) in an amount sufficient to cure the adhesive. The silicone pressure-sensitive adhesive according to claim 1, wherein the phenolic oxidation inhibitor of component (C) is a hindered phenolic oxidation inhibitor. The phenol-modified organosiloxane of component (C) according to claim 1, wherein the phenol-modified organosiloxane is of formula R ³ _a SiO _{(4-a) / 2} wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group,

Hydroxyphenyl containing groups, wherein R ⁴ and R ⁵ are the same or different branched or linear alkyl groups having 1 to 10 carbon atoms, and X is a single bond, oxy group, alkylene group, oxyalkylene group or alkylene Carbonyloxyalkylene group) or a chemical formula

Is a hydroxyphenyl containing group, wherein R ⁴ , R ⁵ and X are as defined above, wherein at least one R ³ in one molecule represents any of the above-mentioned hydroxyphenyl containing groups, and “a” Is 1.5 to 3.0]. The silicone pressure-sensitive adhesive according to claim 1, wherein the aromatic amine type oxidation inhibitor of component (D) is a diphenylamine type oxidation inhibitor or a p-phenylenediamine type oxidation inhibitor. The compound of claim 1, wherein the aromatic amino-modified organopolysiloxane of component (D) is represented by the formula R ⁶ _b SiO _{(4-b) / 2} wherein R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group, formula

Aromatic amino containing group wherein Y is a single bond, oxy group, alkylene group or oxyalkylene group, and "c" is 1 or 2)

Aromatic amino containing group, wherein Y is as defined above, wherein at least one R ⁶ per molecule is any of the aromatic amine containing groups mentioned above, and “b” is 1.5 to 3. Silicone pressure sensitive adhesive. An adhesive tape comprising a film substrate and a silicone pressure-sensitive adhesive layer formed by curing the silicone pressure-sensitive adhesive according to any one of claims 1 to 5 on the film substrate.