JP3235382B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone rubber-based adhesive having good adhesive properties and excellent adhesiveness to an adherend and suitable for use in adhesive tapes, wallpapers, labels and the like. Agent composition.

[0002]

2. Description of the Related Art
Examples of the silicone-based pressure-sensitive adhesive include a silicone pressure-sensitive adhesive comprising a condensate of polysiloxane having _0.5 units of (CH ₃ ) ₃ SiO and SiO ₂ units and dimethylsilicone rubber, and hydrosilyl of an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane. An addition type silicone pressure-sensitive adhesive (JP-B-54-37907, JP-A-63-22886) is known.

However, in the case of a silicone adhesive comprising a polysiloxane having _0.5 units of (CH ₃ ) ₃ SiO and SiO ₂ units and a condensate of dimethyl silicone raw rubber, the curing temperature is 18 due to the use of an organic peroxide for curing.
On the other hand, an addition-type silicone pressure-sensitive adhesive obtained by a hydrosilylation reaction between an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane can be cured at a low temperature. It is necessary to reduce the ratio of the silicon-bonded hydrogen atom to the alkenyl group (hereinafter referred to as H / Vi) in
For this reason, it is difficult for both to exhibit sufficient adhesiveness to the adherend.

Further, an addition type organopolysiloxane composition curable by hydrosilylation exhibits excellent release properties, and an addition type silicone adhesive curable by hydrosilylation has excellent adhesion to a substrate. Although it shows adhesiveness (Japanese Patent Publication No. 53-38751), it is coated on a substrate surface by a method such as coating or screen printing.
It is known that a method such as curing does not exhibit surface tack (or tackiness). In this case, it is known that when H / Vi is reduced by the addition type silicone adhesive, a tackiness due to poor curing occurs, but no adhesion occurs.

[0005] For these reasons, attempts have been made to simultaneously exhibit adhesiveness and tackiness in silicone compositions. However, it is expected that by mixing the addition-type silicone adhesive and the addition-type silicone pressure-sensitive adhesive at an arbitrary ratio, tackiness and adhesiveness can be easily exhibited, but in fact, H / Vi is used as the pressure-sensitive adhesive. Became too large to exhibit any tackiness, and as an adhesive, components required for the development of tackiness had an adverse effect on the strength of the adhesive.

The present invention has been made in view of the above circumstances,
Silicone adhesive that gives a cured product that has sufficient adhesiveness on the surface and good adhesion to the substrate even after coating and curing on the substrate by methods such as coating and screen printing It is intended to provide a composition.

[0007]

Means and Actions for Solving the Problems The present inventor has described
As a result of intensive studies to achieve the objectives described above,
As the silicone rubber-based adhesive composition, (A) the following general group
100 weights of organopolysiloxane represented by the formula (1)
Parts, R¹ _nR^Two _mSiO_{(4-nm) / 2} ... (1) (where R¹Is substituted or unsubstituted without an aliphatic unsaturated bond.
Substituted monovalent hydrocarbon radical, R^TwoIs an alkenyl group,
1.7 ≦ n ≦ 2.2, 0.0002 ≦ m ≦ 0.1, 1.
8 ≦ n + m ≦ 2.3. (B) an organopolicy represented by the following general composition formula (2)
10 to 400 parts by weight of oxane, (R^Three _ThreeSiO_1/2)_x(R^Three _TwoSiO )_y(SiO_Two)_z ... (2) (where R^ThreeIs a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.00001 to 0.000 / g of organopolysiloxane.
0005 moles. Also, x, y and z are respectively
0.25 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.375, 0.25
≤z≤0.667, a number satisfying x + y + z = 1
It is. (C) Fewer hydrogen atoms directly bonded to silicon atoms in one molecule
Organohydrogenpolysiloxanes having at least three
To one total alkenyl group in components (A) and (B)
On the other hand, give 0.5 to 6 hydrogen atoms bonded to silicon atoms.
(D) directly connected to silicon atoms in one molecule
A silicon atom via at least one hydrogen atom and a carbon atom
Epoxy group and / or trialkoxysilicide bonded to
Organosilicon compound having at least one phenyl group
(E) a catalytic amount of platinum or a platinum compound as an essential component.
By doing so, it adheres well to the substrate and
Coating on the substrate by printing, screen printing, etc.
After curing, a cured product with sufficient adhesion on the surface
And found that a pressure-sensitive adhesive composition was obtained.
Invented the invention.

Accordingly, the present invention provides a pressure-sensitive adhesive composition containing the above components (A) to (E) in the above amounts.

Now, the present invention will be described in further detail. The component (A) of the pressure-sensitive adhesive composition of the present invention is an organopolysiloxane represented by the following general formula (1). It has at least two alkenyl groups directly connected to atoms.

R ¹ _n R ² _m SiO _{(4-nm) / 2} (1) (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, R ² Is an alkenyl group,
1.7 ≦ n ≦ 2.2, 0.0002 ≦ m ≦ 0.1, 1.
8 ≦ n + m ≦ 2.3. )

Here, R ¹ preferably has 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-group.
tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, benzyl group, phenyl Aralkyl groups such as ethyl group and phenylpropyl group, and chloromethyl group, bromoethyl group and chloropropyl group in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc. , Trifluoropropyl group, groups such as cyanoethyl group are exemplified,
Among these, it is preferable that all of them are methyl groups or consist of methyl group and phenyl group in view of easiness of synthesis and chemical stability.

The alkenyl group for R ² includes those having 2 to 8 carbon atoms, such as vinyl group, allyl group, propenyl group, isopropenyl group, 1-butenyl group, isobutenyl group, hexenyl group and cyclohexenyl group. Examples thereof include a group and the like, and a vinyl group is most preferable from the viewpoint of ease of synthesis and chemical stability. Further, m and n are as described above, and the organopolysiloxane may be in any form of linear, branched, or network, and may be a mixture thereof. An essentially linear diorganopolysiloxane composed of repeating diorganosiloxane units and having a molecular chain terminal blocked by a triorganosiloxy unit is used. The preferred ranges of m, n, and m + n are respectively 0.001 ≦ m ≦ 0.04,
1.75 ≦ n ≦ 2.1 and 1.85 ≦ n + m ≦ 2.2.

This organopolysiloxane has a viscosity at 25 ° C. of 100 cs or more, usually 100 to 10,000.
000 cs, preferably 1,000 to 1,000,
000 cs is desirable. If it is less than 100 cs, the cured product becomes brittle, and the expression of tackiness may become unstable. In addition, the viscosity is 10,000,000cs
If the ratio exceeds the above range, the amount of the solvent to be diluted increases when coating by a method such as coating or screen printing, which is uneconomical. These siloxanes can be synthesized by a conventionally known method.

Next, the organopolysiloxane of the component (B) is represented by the following general composition formula (2), wherein an alkenyl group is contained in the organopolysiloxane in an amount of 0.00001.
-0.0005 mol / g, preferably 0.00002-
It is generally a resinous material having a three-dimensional structure containing 0.0004 mol / g.

(R^Three _ThreeSiO_1/2)_x(R^Three _TwoSiO )_y(SiO_Two)_z ... (2) (where R^ThreeIs a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.00 g / g of the organopolysiloxane of the component (B)
001 to 0.0005 mol. Also, x, y,
z is 0.25 ≦ x ≦ 0.6 and 0 ≦ y ≦ 0.37, respectively.
5, 0.25 ≦ z ≦ 0.667, and x + y + z = 1
Is a number that satisfies. )

Here, among R ³ , the alkenyl group is the same as R ^2, and the monovalent hydrocarbon group other than the alkenyl group is the same as R ¹ .

X, y, and z are as described above, but are preferably 0.329≤x≤0.545, and 0≤y≤0.214.
5, 0.357 ≦ z ≦ 0.606, and x + y + z =
It is a number that satisfies 1. In this case, x / z (R ³ SiO
_(1/2 unit number / SiO ₂ unit number) is preferably 0.5-1.
5, more preferably 0.65 to 1.2, and when the value of x / z is less than 0.5, the adhesive strength may decrease.
If it exceeds 5, the cohesive strength may decrease.

The alkenyl group content is as described above. If the alkenyl group is less than 0.00001 mol / g, the strength of the cured product decreases, and the adhesiveness decreases. 0.
If it exceeds 005 mol / g, the cured product will not exhibit tackiness.

The amount of the component (B) is 100 parts (A)
Parts (parts by weight, hereinafter the same), 10 to 400 parts, preferably 50 to 200 parts. When less than 10 parts, no tackiness is exhibited, and when more than 400 parts, the viscosity of the composition significantly increases. When coating by a method such as coating, screen printing, etc., a large amount of diluting solvent is required, which is uneconomical and poor in workability.

The organohydrogenpolysiloxane of the component (C) is used in the presence of the component (E) described below in the presence of the component (A),
It is an indispensable component for the addition reaction with the alkenyl group in the component (B) to cure the pressure-sensitive adhesive of the present invention and to give a silicone cured product having practically sufficient strength. It is necessary that the compound has at least three hydrogen atoms bonded to a silicon atom in one molecule, but there is no particular limitation on its molecular structure, and it is conventionally produced, for example, linear, branched, cyclic and tertiary. A variety of original mesh structures are used. Specifically, those represented by the following general composition formula (3) can be suitably used.

R ⁴ _{a Hb} SiO _{(4-ab) / 2} (3)

Here, R ⁴ is the same as that exemplified above for R ¹ and R ² , which has 1 to 10 carbon atoms bonded to a silicon atom.
Are preferably substituted or unsubstituted monovalent hydrocarbon groups, particularly those containing no aliphatic unsaturated bond, and are preferably alkyl groups such as methyl group, ethyl group and propyl group, and aryl groups such as phenyl group and tolyl group. And monovalent hydrocarbon groups having 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, such as a cycloalkyl group such as a cyclohexyl group. Among them, it is preferable that all of them are a methyl group or a methyl group and a phenyl group as in the case of the component (A). A, b and a + b are 1.6 ≦ a ≦
It is a number that satisfies 2.2, 0.002 ≦ b ≦ 1, 1.6 <a + b ≦ 3.

The viscosity of the organohydrogenpolysiloxane (C) at 25 ° C. is from 1 to 1,000.
cs, particularly preferably 5 to 200 cs. If the viscosity exceeds 1,000 cs, the compatibility with the components (A) and (B) may deteriorate.

The amount of component (C) used is such that the amount of hydrogen atoms bonded to silicon atoms in component (C) is 0.5 to 6 per alkenyl group in components (A) and (B). It is an amount equivalent to an equivalent, and preferably an amount equivalent to 1 to 3 equivalents. When the amount is less than 0.5 equivalent, the mechanical strength of the cured product and the adhesiveness to the substrate are inferior. When the amount exceeds 6 equivalents, foaming is liable to occur during curing.

The organosilicon compound of the component (D) in the present invention can be added to a tacky adhesive by blending it.
It is a component that imparts adhesion to metals such as iron, aluminum, nickel, etc., polyamide-based films, polyester-based films, paper, nonwoven fabrics, thermoplastic elastomers and polyurethane sheets, and is an essential component in the present invention.

This organic silicon compound has at least one, preferably two, hydrogen atoms bonded to a silicon atom in one molecule.
Any compound may be used as long as it is an organosilicon compound having at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom directly bonded to the silicon atom or more. Those having a cyclic polysiloxane skeleton are preferred from the viewpoint of easiness. In the case of a cyclic polysiloxane skeleton, the number of silicon atoms forming a siloxane ring is 3 to 6, preferably 4, for ease of synthesis. On the other hand, in the case of the linear shape, if the molecular weight is large, the viscosity becomes high and the synthesis and handling become inconvenient. Therefore, about 5 to 50 silicon atoms forming the siloxane chain are desirable, but it is particularly limited to this. Not something.

Hydrogen atom bonded to silicon atom (SiH group)
Is preferably bonded to a silicon atom in the middle of the molecular chain, that is, a silicon atom of a bifunctional siloxane unit represented by = SiO _2/2 , and the organic group bonded to the silicon atom is R ¹ , similar preferred as R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms excluding an aliphatic unsaturated bond, in particular a methyl group, a phenyl group, and the like.

Examples of the epoxy group bonded to the silicon atom via a carbon atom such as an alkylene group include, for example, those represented by the following formulas. The alkoxy group in the trialkoxysilyl group includes a methoxy group, Examples thereof include those having 1 to 4 carbon atoms such as an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group.

[0029]

Embedded image

These compounds can be prepared by a conventional method using an organic compound having an alkenyl group and an epoxy group and / or a trialkoxysilyl group in an organohydrogenpolysiloxane having three or more hydrogen atoms bonded to a silicon atom in one molecule. And by subjecting it to a partial addition reaction. After the completion of the reaction, a mixture obtained by removing the unreacted product and the catalyst for the addition reaction may be used, but it is preferable to isolate and use the desired product.

Specific examples of the organic silicon compound used as the component (D) include the following compounds.

[0032]

Embedded image

The amount of the component (D) used is 100 parts of the component (A).
The range is 0.1 to 20 parts, preferably 0.5 to 10 parts per part. If the amount is less than 0.1 part, sufficient adhesive strength cannot be obtained. If the amount exceeds 20 parts, the mechanical properties of the cured product deteriorate, and foaming is likely to occur during curing.

The platinum catalyst of the component (E) used in the present invention may be a known catalyst usually used for hydrosilation, and may be platinum black, chloroplatinic acid, an alcohol-modified chloroplatinic acid, platinum or the like. Examples include complexes with olefins or aldehydes, complexes of platinum with vinyl siloxane, and the like.

The amount of the component (E) used is a catalytic amount.
It may be appropriately adjusted according to the desired curing speed, but is preferably 0.5 to 500 ppm, preferably 0.5 to 500 ppm by weight of platinum atom with respect to the total amount of the above components (A), (B), (C) and (D). It is in the range of 1 to 250 ppm. If it is less than 0.5 ppm, poor curing is likely to occur, and a high temperature and a long time are required for curing. If it exceeds 500 ppm, not only is it difficult to control the curing reaction, but also disadvantageous in cost.

It is recommended that the adhesive of the present invention contains reinforcing silica. This reinforcing silica is a component for reinforcing the mechanical strength of the cured product, and may be a known one conventionally used for silicone rubber, for example, fumed silica, precipitated silica, crystalline silica, calcined silica, There are quartz powder, diatomaceous earth and the like, which may be used alone or in combination of two or more. Such reinforcing silica may be used as it is, but in order to impart good fluidity to the adhesive, the surface thereof is treated with an organic silicon compound such as methylchlorosilanes, dimethylpolysiloxane, and hexamethyldisilazane. Is preferably used. The amount of the reinforcing silica to be used is as follows.
The amount is preferably from 0 to 200 parts, more preferably from 3 to 150 parts, per part. If the amount exceeds 200 parts, the fluidity of the composition may be reduced and workability may be deteriorated.

The tacky adhesive of the present invention has a component other than the above components.
Heat resistance improver, flame retardant improver, adhesion promotion
An accelerator, a reaction control agent and the like may be blended. Also other species
Further organopolysiloxanes may be further incorporated. This
Additives that may be added additionally, such as
For example, carbon, NiO_Two, FeO , FeO_Two, Fe_TwoO_Three,
Fe_ThreeO_Four, Co O_Two, CeO_TwoAnd TiO_TwoChosen from
Heat and flame retardant improver, benzotriazole, benz
Flame retardant such as imidazole, vinyl trimethoxy
Silane, 3-methacryloxypropyltrimethoxysila
3-acryloxypropyltrimethoxysilane, 3
-Adhesion of glycidoxypropyltrimethoxysilane etc.
Accelerator, methylvinylcyclopolysiloxane, acetylene
Alcohols and triallyl isocyanurate
Control agent, such as non-functional dimethylpolysiloxane.
Plasticizers, viscosity modifiers, etc._Two, R^Three _ThreeS
iO_1/2Unitless and soluble in silicone oil
A functional silicone resin can also be used. These appendages
The amount of the additive used is arbitrary as long as the effect of the present invention is not impaired.
It is.

The pressure-sensitive adhesive of the present invention is prepared by mixing (A), (B), (C) and (E) with all of the above-mentioned components, or (A) due to (A) during storage. ),
In some cases, the reaction between the component (B) and the component (C) progresses and curing starts. Therefore, an effective reaction control agent, for example, triallyl isocyanurate, acetylene alcohol, or the like is added, or the whole is stored in two groups, that is, a main agent and a curing agent, and all components are uniformly used at the time of use. It is recommended to mix. The combination of the two groups is not particularly limited except that the components (A), (B), (C) and (E) are not allowed to coexist in the same group. For example, the combination of the components (A) to (D) This is a method of dividing into components (E), a method of using a part of the components (A) and (B), the component (E) as a main agent, and the components (C) and (D) as a curing agent.

This tacky adhesive is desirably used without solvent, but may be diluted with various organic solvents for the purpose of improving coatability and controlling film thickness. Specifically, toluene, xylene, ethylbenzene, hexane, heptane, octane, mineral spirit, hexamethyldisiloxane,
One or more of octamethylcyclotetrasiloxane, ethyl acetate, methyl ethyl ketone and the like can be used, and the organic solvent is not particularly limited as long as it does not inhibit the addition reaction.

The above adhesive composition has a viscosity at 25 ° C. of 1 to 200,000 cs, particularly 10 to 100, cs.
It is preferably in the range of 000 cs.

The pressure-sensitive adhesive composition of the present invention may be, for example, a thin metal film of iron, aluminum, nickel or the like, a polyamide film, a polyester film, paper, nonwoven fabric,
Coating on substrates such as thermoplastic elastomer sheets and polyurethane sheets. In this case, the coating method is coating,
Methods such as impregnation, spraying, and screen printing can be employed. In addition, after application | coating, it can be hardened | cured by heating at 60-180 degreeC normally for 0.1 to 10 minutes.

[0042]

The pressure-sensitive adhesive composition of the present invention, unlike the conventional addition-type silicone pressure-sensitive adhesive, exhibits sufficient adhesiveness as an adherend and cannot be obtained with the conventional addition-type silicone adhesive. Surface tackiness can be developed.

[0043]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts indicate parts by weight,
Me and Vi represent a methyl group and a vinyl group, respectively.

Example 1 50 parts of dimethylpolysiloxane capped at both ends by dimethylvinylsiloxy group having a viscosity at 25 ° C. of 100,000 cs and having an average molecular formula (II) represented by the following average molecular formula (I) 50 parts of methyl vinyl polysiloxane resin, 16 parts of surface-treated silica,
1.6 parts of methyl hydrogen polysiloxane containing an epoxy group and a trimethoxysilylethyl group represented by the following molecular formula (III), 2.0 parts of methyl hydrogen polysiloxane represented by the following average molecular formula (IV), and a platinum catalyst 0.4 part of a 1% concentration by weight of platinum atom of a platinum / vinylsiloxane complex-terminated dimethylvinylsiloxy group-blocked dimethylpolysiloxane solution was mixed with 25 parts by weight of 25%.
A mixture having a viscosity of 20,000 poise at C was obtained.

Further, this was dissolved in 50 parts of toluene to obtain a solution having a viscosity of 500 poise. This solution is 50 μm thick
PET film was coated using a bar coater,
When cured at 20 ° C. for 3 minutes, a uniform coated surface having a thickness of 50 μm was obtained.

[0046]

Embedded image (However, n is a number that satisfies the above or below viscosities, respectively.)

[0047]

Embedded image (However, x, y, and z are respectively x: y: z = 33: 1:
X + y + z = 1, vinyl group content 0.0
002 mol / g. )

[0048]

Embedded image (Viscosity at 25 ° C. 12 cs)

Example 2 Dimethylvinylsiloxane-blocked dimethylpolysiloxane 6 represented by the above average molecular formula (I) and having a viscosity of 30,000 cs at 25 ° C.
0 parts, 40 parts of methylvinylpolysiloxane resin represented by the following average composition formula (V), 10 parts of surface-treated silica, and methyl hydrogen polysiloxane 1 containing epoxy group and trimethoxysilylethyl group represented by the above molecular formula (III) 0.6 parts, and 2.0 parts of methyl hydrogen polysiloxane represented by the above average molecular formula (IV), and a dimethylvinylsiloxy group-blocked dimethyl terminal at both ends of a platinum / vinylsiloxane complex having a concentration of 1% by weight of platinum as a platinum catalyst. 0.3 part of the polysiloxane solution was mixed to obtain a mixture having a viscosity of 1,200 poise at 25 ° C.

Further, this was dissolved in 20 parts of toluene to obtain a solution having a viscosity of 450 poise. This mixture was coated on a PET film having a thickness of 50 μm in the same manner as in Example 1, and cured at 120 ° C. for 3 minutes.
Was obtained.

[0051]

Embedded image (Where w, x, y, and z are respectively w: x: y: z = 4
Expressed as a ratio of 0: 1: 8: 45, w + x + y + z = 1,
This is a number that gives a vinyl group content of 0.00015 mol / g. )

Comparative Example 1 80 parts of dimethylpolysiloxane capped at both ends by dimethylvinylsiloxy group having a viscosity at 25 ° C. of 100,000 cs and having the average molecular formula (I), and having the following average composition formula (VI) 20 parts of methyl vinyl polysiloxane resin, 16 parts of surface-treated silica,
2.0 parts of an epoxy group- and trimethoxysilyl group-containing methyl hydrogen polysiloxane represented by the above molecular formula (III), 2.0 parts methyl hydrogen polysiloxane represented by the above average molecular formula (IV), and platinum as a platinum catalyst 0.2 part of a dimethylpolysiloxane solution having a 1% concentration of atomic weight of a platinum / vinylsiloxane complex and a dimethylvinylsiloxy group at both ends was mixed to obtain a mixture having a viscosity of 8,000 poise at 25 ° C.

Further, 100 parts of this mixture was mixed with 40 parts of toluene.
The resulting solution was diluted with the solution to obtain a solution having a viscosity of 400 poise. Example 1
Was coated on a PET film having a thickness of 50 μm in the same manner as described above, but no stickiness was produced on the surface.

[0054]

Embedded image (Where x, y, and z are x: y: z = 666: 1, respectively)
It is represented by the ratio of 00: 900, and is a number such that x + y + z = 1 and the amount of the vinyl group is 0.00085 mol / g. )

[Comparative Example 2] 43 parts of dimethylpolysiloxane having a number-average degree of polymerization of 8,000 and capped with dimethylvinylsiloxy groups at both terminals, represented by the above average molecular formula (I), and methyl represented by the following average composition formula (VII) A mixture of 57 parts of the polysiloxane resin and 167 parts of toluene was heated and stirred at 110 ° C. for 3 hours, and then cooled to obtain a viscous solution. With respect to 100 parts of the solid content of this solution, the following average molecular formula (VII) was used.
0.1 part of methylhydrogenpolysiloxane represented by I) and 3.3 parts of a 0.5% (in terms of platinum atom weight) isopropyl alcohol solution of chloroplatinic acid were mixed,
A silicone solution having a nonvolatile content of 60% was obtained.

This was applied in the same manner as in Example 1 to a thickness of 50 μm.
m of PET film was coated. Although a strong adhesive surface was obtained on the surface, the film was not adhered.

[0057]

Embedded image (However, x and z are each represented by a ratio of x: z = 3: 4, and are numbers that satisfy x + z = 1.)

[0058]

Embedded image (Viscosity at 25 ° C. 20 cs)

Example 3 A dimethylpolysiloxane 4 having the average molecular formula (I) and having a viscosity of 10,000 cs at 25.degree.
0 parts, 60 parts of a methylvinylpolysiloxane resin represented by the above average composition formula (II), 10 parts of surface-treated silica, 2.0 parts of an epoxy group-containing methylhydrogenpolysiloxane represented by the following molecular formula (IX), and 2.0 parts of methylhydrogenpolysiloxane represented by the average molecular formula (IV), a platinum / vinylsiloxane complex having a concentration of 1% by weight of platinum atom as a platinum catalyst, and a dimethylpolysiloxane solution having a dimethylvinylsiloxy group at both ends thereof 0.2%. The parts were mixed to obtain a mixture having a viscosity of 600 poise at 25 ° C.

This mixture was coated on a 420 denier nylon 66 cloth as a fiber substrate and cured by heating at 150 ° C. for 1 minute. The obtained coated product was uniform, and the thickness of the silicone film was 50 μm.

[0061]

Embedded image

[Comparative Example 3] A dimethylpolysiloxane 1 having the above average molecular formula (I) and having a viscosity of 10,000 cs at 25 ° C. and capped at both ends with dimethylvinylsiloxy groups.
00 parts, 10 parts of surface-treated silica, 2.0 parts of an epoxy group-containing methylhydrogenpolysiloxane represented by the above-mentioned molecular formula (IX), and 2.0 parts of an organohydrogenpolysiloxane represented by the above-mentioned average molecular formula (IV), As a platinum catalyst, 0.2 part of a dimethylpolysiloxane solution having a 1% concentration by weight of platinum atom and a dimethylvinylsiloxy group at both ends of a platinum / vinylsiloxane complex mixed and mixed with 25 parts
At 350C, a mixture having a viscosity of 350 poise was obtained.

This mixture was coated on a 420 denier nylon 66 cloth as a fiber base and cured by heating at 150 ° C. for 1 minute. The obtained coated product was uniform, and the thickness of the silicone film was 50 μm, but no tackiness was exhibited on the surface.

The mixture (adhesive composition) obtained in each example was evaluated for adhesiveness and tackiness by the following methods. Table 1 shows the results. Adhesion: 120 ° C / PET resin or 66 nylon resin
After curing for 1 hour and leaving it at room temperature for 1 day, it has a tensile strength of 50
The shear adhesion was measured at mm / min. Adhesion: Using a 50 μm-thick PET film or 420 denier nylon 66 cloth as a substrate, a roller (weight: 2,000 ± 50 covered with a rubber layer having a thickness of about 6 mm)
g of metal) was reciprocated once at a compression speed of 300 mm / min, left at room temperature for one day, and then peeled off at a speed of 300 mm / min in a 180 ° direction.

[0065]

[Table 1]

From the results shown in Table 1, it was confirmed that the adhesive composition of the present invention was excellent in adhesiveness and adhesiveness.

Continuation of the front page (56) References JP-A-2-298549 (JP, A) JP-A-4-246466 (JP, A) JP-A-62-156163 (JP, A) JP-A-2-75681 (JP) JP-A-2-225566 (JP, A) JP-A-3-37265 (JP, A) JP-A-1-36651 (JP, A) JP-A-5-194930 (JP, A) 5-271548 (JP, A) JP-A-6-316690 (JP, A) JP-A-7-70542 (JP, A) JP-A-7-157744 (JP, A) JP-B-53-21026 (JP, A) B2) Japanese Patent Publication No. 59-5219 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 183/04 C09J 7/02

Claims (1)

(57) [Claims] (A) represented by the following general composition formula (1)
100 parts by weight of organopolysiloxane, R¹ _nR^Two _mSiO_{(4-nm) / 2} ... (1) (where R¹Is substituted or unsubstituted without an aliphatic unsaturated bond.
Substituted monovalent hydrocarbon radical, R^TwoIs an alkenyl group,
1.7 ≦ n ≦ 2.2, 0.0002 ≦ m ≦ 0.1, 1.
8 ≦ n + m ≦ 2.3. (B) an organopolicy represented by the following general composition formula (2)
10 to 400 parts by weight of oxane, (R^Three _ThreeSiO_1/2)_x(R^Three _TwoSiO )_y(SiO_Two)_z ... (2) (where R^ThreeIs a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.00001 to 0.000 / g of organopolysiloxane.
0005 moles. Also, x, y and z are respectively
0.25 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.375, 0.25
≤z≤0.667, a number satisfying x + y + z = 1
It is. (C) Fewer hydrogen atoms directly bonded to silicon atoms in one molecule
Organohydrogenpolysiloxanes having at least three
To one total alkenyl group in components (A) and (B)
On the other hand, give 0.5 to 6 hydrogen atoms bonded to silicon atoms.
(D) directly connected to silicon atoms in one molecule
A silicon atom via at least one hydrogen atom and a carbon atom
Epoxy group and / or trialkoxysilicide bonded to
Organosilicon compound having at least one phenyl group
0 parts by weight, (E) containing catalytic amount of platinum or platinum compound
A pressure-sensitive adhesive composition comprising: