JPH08134427A - Hardenable pressure-sensitive adhesive composition - Google Patents

Abstract

PURPOSE: To improve the surface stickiness and adhesion to a substrate after the application and curing of a hardenable pressure-sensitive adhesive compsn. by compounding specific organopolysiloxanes, another organosilicon compd., and a platinum catalyst. CONSTITUTION: This compsn. contains 100 pts.wt. organopolysiloxane represented by formula I (wherein R<1> is a monovalent hydrocarbon group; R<2> is alkenyl; 1.7<=n<=2.2; 0.0002<=m<=0.1; and 1.8<=n+m<=2.3), 10-400 pts.wt. organopolysiloxane represented by formula II [wherein R<3> is a monovalent hydrocarbon group provided that part of R<3> ' s (in an amt. of 0.00001-0.0005mol based on 1 g of the organopolysiloxane) are alkenyl; 0.25<=x<=0.6; 0<=y<=0.375; 0.25<=z<=0.667; and x+y+z=1], an organohydrogenpolysiloxane having at least three hydrogen atoms directly bonded to silicon atoms in the molecule, 0.1-20 pts.wt. organosilicon compd. having at least one hydrogen atom directly bonded to a silicon atom and at least one epoxy and/or trialkoxysilyl group in the molecule, and a catalytic amt. of platinum or a platinum compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a good adhesive property and also exhibits excellent adhesiveness to an adherend, and is a silicone rubber-based adhesive adhesive suitable for applications such as adhesive tapes, wallpapers and labels. Agent composition.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Examples of the silicone-based adhesive include a silicone adhesive composed of a condensate of polysiloxane having (CH ₃ ) ₃ SiO _0.5 unit and SiO ₂ unit and dimethyl silicone raw rubber, and an alkenyl group-containing organopolysiloxane and hydrosilyl of organohydrogenpolysiloxane. Addition type silicone adhesives by chemical reaction (Japanese Patent Publication No. 54-37907, Japanese Patent Laid-Open No. 63-22886) are known.

However, the silicone pressure-sensitive adhesive comprising a condensate of polysiloxane having (CH ₃ ) ₃ SiO _0.5 units and SiO ₂ units and dimethyl silicone raw rubber has a curing temperature of 18 because of the use of organic peroxide for curing.
On the other hand, addition type silicone adhesives obtained by hydrosilylation reaction of alkenyl group-containing organopolysiloxanes and organohydrogenpolysiloxanes can be cured at low temperatures, but their adhesiveness is expressed, so that the system is high. It is necessary to reduce the ratio of silicon atom-bonded hydrogen atoms to alkenyl groups (hereinafter, referred to as H / Vi) in
Therefore, it is difficult for both of them to exhibit sufficient adhesiveness with the adherend.

Further, the addition type organopolysiloxane composition curable by hydrosilylation exhibits excellent releasability, and the addition type silicone adhesive curable by hydrosilylation is excellent for a substrate. After exhibiting adhesiveness (Japanese Patent Publication No. 53-38751), after coating the surface of the substrate by a method such as coating or screen printing,
It is known that surface tack (or tackiness) is not exhibited by a method such as curing. In this case, it is known that when H / Vi is lowered with an addition type silicone adhesive, a tackiness due to defective curing occurs, but no adhesion occurs.

Under these circumstances, attempts have been made to simultaneously develop adhesiveness and tackiness in silicone-based compositions. However, it is expected that tackiness and adhesiveness can be easily expressed by mixing the addition-type silicone adhesive and the addition-type silicone pressure-sensitive adhesive in an arbitrary ratio. Was too large to exhibit tackiness at all, and as an adhesive, the components necessary for developing tackiness adversely affect 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 tackiness on the surface even after being applied and cured on a substrate by a method such as coating or screen printing, and that gives a cured product that exhibits good adhesion to the substrate It is intended to provide a composition.

[0007]

The inventor of the present invention has
As a result of diligent study to achieve the purpose
As a silicone rubber adhesive composition, (A) the following general group
100-fold organopolysiloxane represented by formula (1)
Quantity part, R¹ _nR² _mSiO_{(4-nm) / 2} (1) (where R is¹Is a substituted or non-aliphatic unsaturated bond
Substituted monovalent hydrocarbon group, R²Is an alkenyl group,
1.7 ≦ n ≦ 2.2, 0.0002 ≦ m ≦ 0.1, 1.
8 ≦ n + m ≦ 2.3. ) (B) Organopolish represented by the following general composition formula (2)
10-400 parts by weight of roxane, (R³ ₃SiO_1/2)_x(R³ ₂SiO )_y(SiO₂)_z (2) (where R is³Is a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.00001 to 0. per 1 g of organopolysiloxane.
Contains 0005 moles. Also, x, y and z are respectively
0.25 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.375, 0.25
A number that satisfies ≦ z ≦ 0.667 and satisfies x + y + z = 1.
Is. ) (C) Fewer hydrogen atoms directly bonded to silicon atoms in one molecule
Organohydrogenpolysiloxane with 3
To one total alkenyl group in the components (A) and (B)
In contrast, give 0.5 to 6 hydrogen atoms bonded to silicon atoms
(D) directly bonded to silicon atom in one molecule
At least one hydrogen atom and silicon atom through the carbon atom
Epoxy group and / or trialkoxysilyl bonded to child
0.1 to 2 organosilicon compound having at least one ruthel group
0 parts by weight, (E) A catalytic amount of platinum or a platinum compound is used as an essential component.
By forming the adhesive, it adheres well to the base material and
Coating on the substrate by coating, screen printing, etc.
After curing, a cured product with sufficient tackiness on the surface
It was found that a tacky adhesive composition giving
Invented.

Accordingly, the present invention provides a tacky adhesive composition containing the above components (A) to (E) in the above amount.

The present invention will be described in more detail below. The component (A) of the tacky adhesive composition of the present invention is an organopolysiloxane represented by the following general composition formula (1), and silicon is contained in one molecule. It has at least two alkenyl groups directly attached to an atom.

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, as R ¹ , those having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms are preferable, and methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t
ert-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 some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano group and the like. Examples include groups such as a trifluoropropyl group and a cyanoethyl group.
Of these, from the viewpoint of easiness of synthesis and chemical stability, it is preferable that they are all methyl groups or consist of a methyl group and a phenyl group.

Examples of the alkenyl group represented by R ² include 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 vinyl groups, but vinyl groups are most preferable from the viewpoint of ease of synthesis and chemical stability. Further, m and n are as described above, and the organopolysiloxane may have any of linear, branched, and net forms, and may be a mixture thereof, but the main chain portion is usually An essentially linear diorganopolysiloxane is used which is composed of repeating diorganosiloxane units and whose molecular chain ends are capped with triorganosiloxy units. The preferable ranges of m, n and m + n are 0.001 ≦ m ≦ 0.04,
1.75 ≦ n ≦ 2.1 and 1.85 ≦ n + m ≦ 2.2.

The organopolysiloxane has a viscosity at 25 ° C. of 100 cs or more, usually 100 to 10,000.
20,000 cs, preferably 1,000-1,000,
It is desirable to be 000 cs. If it is less than 100 cs, the cured product becomes brittle and the development of tackiness may become unstable. Also, the viscosity is 10,000,000 cs
If it exceeds, the amount of the solvent to be diluted becomes large when applied by a method such as coating or screen printing, which is uneconomical. Incidentally, these siloxanes can be synthesized by a conventionally known method.

Next, the organopolysiloxane as the component (B) is represented by the following general composition formula (2), and an alkenyl group of 0.00001 is contained in the organopolysiloxane.
~ 0.0005 mol / g, preferably 0.00002 ~
It is generally resin-like and has a three-dimensional structure containing 0.0004 mol / g.

(R³ ₃SiO_1/2)_x(R³ ₂SiO )_y(SiO₂)_z (2) (where R is³Is a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.001 g of the organopolysiloxane of the component (B)
001 to 0.0005 mol is contained. 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. )

Of R ³ , the alkenyl group is the same as R ² above, and the monovalent hydrocarbon group other than the alkenyl group is the same as R ¹ above.

X, y and z are as described above, but 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 to 1.
5, more preferably 0.65 to 1.2, and if the value of x / z is less than 0.5, the adhesive strength may decrease, and
If it exceeds 5, the cohesive force may decrease.

The alkenyl group content is as described above, and if the alkenyl group content is less than 0.00001 mol / g, the strength of the cured product will decrease and the adhesiveness will decrease. 0.
If it is more than 005 mol / g, the tackiness of the cured product will not be exhibited.

The blending amount of the component (B) is 100 parts of the component (A).
10 to 400 parts, preferably 50 to 200 parts, relative to 10 parts by weight (the same applies hereinafter), if less than 10 parts does not develop tackiness, and if more than 400 parts the viscosity of the composition increases significantly. When coating by a method such as coating, screen printing, etc., a large amount of a diluting solvent is required, which is uneconomical and inferior in workability.

The organohydrogenpolysiloxane as the component (C) is prepared by reacting the (A) component in the presence of the component (E) described below.
It is an essential component for addition-reacting with the alkenyl group in the component (B) to cure the tacky adhesive of the present invention and to give a silicone cured product having practically sufficient strength. This product needs to have at least three hydrogen atoms bonded to silicon atoms in one molecule, but its molecular structure is not particularly limited, and it is conventionally produced, for example, linear, branched, cyclic and tertiary. Various original mesh structures are used. Specifically, those represented by the following general composition formula (3) can be preferably used.

R ⁴ _a H _b SiO _{(4-ab) / 2} (3)

Here, R ⁴ is the same as the one exemplified as R ¹ and R ² and has 1 to 10 carbon atoms bonded to a silicon atom.
A substituted or unsubstituted monovalent hydrocarbon group, which is particularly preferably one containing no aliphatic unsaturated bond, is an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl such as a phenyl group or a tolyl group. Groups, cycloalkyl groups such as cyclohexyl groups and the like, and monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Of these, it is preferable that all of them are methyl groups or that they are composed of a methyl group and a phenyl group, like the component (A). Further, a, b, and a + b are 1.6 ≦ a ≦
It is a number that satisfies 2.2, 0.002 ≦ b ≦ 1, and 1.6 <a + b ≦ 3.

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

The amount of the component (C) used is such that the amount of hydrogen atoms bonded to silicon atoms in the component (C) is 0.5 to 6 with respect to one alkenyl group in the components (A) and (B). The amount is equivalent, and preferably 1 to 3 equivalent. If it is less than 0.5 equivalent, the mechanical strength of the cured product and the adhesiveness to the substrate are poor, and if it exceeds 6 equivalent, foaming tends to occur during curing.

The organosilicon compound as the component (D) in the present invention is blended with it to form a tacky adhesive.
It is a component that imparts adhesiveness to metals such as iron, aluminum and nickel, polyamide-based films, polyester-based films, paper, non-woven fabrics, thermoplastic elastomers or polyurethane sheets, and is an essential component in the present invention.

This organosilicon compound has at least one hydrogen atom bonded to a silicon atom, preferably 2 hydrogen atoms per molecule.
Any compound may be used as long as it is an organic silicon compound having at least one epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom directly bonded to at least one and a silicon atom, Those having a cyclic polysiloxane skeleton are preferable from the viewpoint of easiness. In the case of the cyclic polysiloxane skeleton, the number of silicon atoms forming the siloxane ring is 3 to 6, preferably 4 because of easy synthesis. On the other hand, in the case of a linear form, if the molecular weight is large, the viscosity becomes high and the synthesis and handling become inconvenient. Therefore, it is desirable that the number of silicon atoms forming the siloxane chain is about 5 to 50, but it is particularly limited. Not a thing.

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

Examples of the epoxy group bonded to a silicon atom via a carbon atom such as an alkylene group include those represented by the following formulas, and the alkoxy group in the trialkoxysilyl group is 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

As these compounds, an organic compound having an alkenyl group and an epoxy group and / or a trialkoxysilyl group in an organohydrogenpolysiloxane having hydrogen atoms bonded to three or more silicon atoms in one molecule is used in a conventional method. It is manufactured by carrying out a partial addition reaction according to. After completion of the reaction, a mixture obtained by only removing the unreacted material and the catalyst for addition reaction may be used, but it is preferable to isolate the desired product and use it.

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

[0032]

Embedded image

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

The component (E) platinum catalyst used in the present invention may be a known one usually used for hydrosilation, such as platinum black, chloroplatinic acid, alcohol modified chloroplatinic acid, and platinum. Examples thereof include a complex with an olefin or an aldehyde and a complex with platinum and vinyl siloxane.

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

It is recommended to add reinforcing silica to the tacky adhesive of the present invention. This reinforcing silica is a component for reinforcing the mechanical strength of a cured product, and may be a known one conventionally used for silicone rubber, for example, fumed silica, precipitated silica, crystalline silica, calcined silica, Examples thereof include quartz powder and diatomaceous earth, and these may be used alone or in combination of two or more kinds. Such reinforcing silica may be used as it is, but in order to impart good fluidity to the pressure-sensitive adhesive, its surface is treated with an organosilicon compound such as methylchlorosilanes, dimethylpolysiloxane and hexamethyldisilazane. It is preferable to use the one treated with. The amount of the reinforcing silica used is 100 parts (A).
The amount may be 0 to 200 parts, preferably 3 to 150 parts. If it exceeds 200 parts, the fluidity of the composition may be lowered and the workability may be deteriorated.

The tacky adhesive of the present invention contains other than the above components.
Also, if necessary, heat resistance improver, flame retardant improver, adhesion promotion
You may mix | blend a promoter, a reaction control agent, etc. Also other species
You may further mix | blend the organopolysiloxane of the class. This
As an additive that may be added additionally, such as
For example, carbon, NiO₂, FeO , FeO₂, Fe₂O₃,
Fe₃O_Four, Co O₂, CeO₂And TiO₂Chosen from
Heat resistance and flame retardancy improver, benzotriazole, benz
Flame retardant improvers such as imidazole, vinyltrimethoxy
Silane, 3-methacryloxypropyltrimethoxysila
3-acryloxypropyltrimethoxysilane, 3
-Adhesion of glycidoxypropyltrimethoxysilane, etc.
Accelerator, methyl vinyl cyclopolysiloxane, acetylene
Alcohols, triallyl isocyanurate, etc.
Response control agent, such as non-functional dimethyl polysiloxane
Basically SiO such as plasticizer and viscosity modifier₂, R³ ₃S
iO_1/2Made of units, and is soluble in silicone oil
It is also possible to use a functional silicone resin. These
The amount of the additive used is arbitrary as long as it does not impair the effects of the present invention.
Be done.

The tacky adhesive of the present invention contains (A), (B), (C) and (E) in the mixed state of all the above-mentioned components, particularly (A) during storage. ),
In some cases, the reaction between the component (B) and the component (C) proceeds to start curing. Therefore, effective reaction control agents such as triallyl isocyanurate, acetylene alcohols, etc. are added, or the whole is divided into two groups, that is, divided into a main agent and a curing agent, and stored, and all components are made uniform at the time of use. Mixing is recommended. The combination divided into two groups is not particularly limited except that the components (A), (B), (C) and (E) do not coexist in the same group, but for example, the components (A) to (D) The method is to divide it into the component (E), a part of the components (A) and (B), the component (E) as a main component, and the components (C) and (D) as a curing agent.

This tacky adhesive is preferably used without solvent, but may be diluted with various organic solvents for the purpose of improving coatability and controlling the film thickness. Specifically, toluene, xylene, ethylbenzene, hexane, heptane, octane, mineral spirits, hexamethyldisiloxane,
One or more of octamethylcyclotetrasiloxane, ethyl acetate, methyl ethyl ketone and the like can be used, and there is no particular limitation as long as it is an organic solvent that does not inhibit the addition reaction.

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

The tacky adhesive composition of the present invention may be a thin metal film of iron, aluminum, nickel, etc., a polyamide film, a polyester film, paper, a nonwoven fabric,
It is applied to base materials 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 adopted. In addition, after coating, it can be normally cured by heating at 60 to 180 ° C. for 0.1 to 10 minutes.

[0042]

EFFECTS OF THE INVENTION The tacky adhesive composition of the present invention, unlike conventional addition-type silicone adhesives, exhibits sufficient adhesiveness as an adherend and cannot be obtained by conventional addition-type silicone adhesives. Surface tackiness can be expressed.

[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 by weight of dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends and having a viscosity of 100,000 cs at 25 ° C., represented by the following average molecular formula (I), and represented by the following average composition formula (II). 50 parts of methyl vinyl polysiloxane resin, 16 parts of surface-treated silica,
Epoxy group- and trimethoxysilylethyl group-containing methyl hydrogen polysiloxane represented by the following molecular formula (III): 1.6 parts, methyl hydrogen polysiloxane represented by the following average molecular formula (IV): 2.0 parts, as a platinum catalyst A 0.4% solution of a dimethylpolysiloxane having dimethylvinylsiloxy groups at both ends blocked with a platinum / vinylsiloxane complex having a concentration of 1% by weight of platinum atoms was mixed to obtain 25
A mixture having a viscosity of 20,000 poise at 0 ° C. was obtained.

Further, this was dissolved in 50 parts of toluene to obtain a solution having a viscosity of 500 poise. This solution has a thickness of 50 μm
Coat the PET film with a bar coater to 1
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 viscosity.)

[0047]

[Chemical 4] (However, x, y, and z are x: y: z = 33: 1:
It is represented by the ratio of 38, x + y + z = 1, vinyl group content 0.0
The number is 002 mol / g. )

[0048]

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

Example 2 A dimethylpolysiloxane 6 having a dimethylvinylsiloxy group at both ends and having a viscosity of 30,000 cs at 25 ° C., represented by the above average molecular formula (I).
0 part, 40 parts of methylvinylpolysiloxane resin represented by the following average composition formula (V), 10 parts of surface-treated silica, epoxy group- and trimethoxysilylethyl group-containing methylhydrogenpolysiloxane 1 represented by the above formula (III). .6 parts, and 2.0 parts of methylhydrogenpolysiloxane represented by the above average molecular formula (IV), and 1% concentration of platinum / vinylsiloxane complex as a platinum catalyst at both ends of dimethylvinylsiloxy group-blocked dimethyl of platinum / vinylsiloxane complex. 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 to give a thickness of 50 μm.
A uniform coating surface was obtained.

[0051]

[Chemical 6] (However, w, x, y, and z are w: x: y: z = 4, respectively.
Expressed as a ratio of 0: 1: 8: 45, w + x + y + z = 1,
The number is such that the vinyl group content is 0.00015 mol / g. )

Comparative Example 1 80 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends and having a viscosity of 100,000 cs at 25 ° C., represented by the above average molecular formula (I), represented by the following average composition formula (VI). 20 parts of methyl vinyl polysiloxane resin, 16 parts of surface-treated silica,
2.0 parts of a methylhydrogenpolysiloxane containing an epoxy group and a trimethoxysilyl group represented by the molecular formula (III), 2.0 parts of a methylhydrogenpolysiloxane represented by the average molecular formula (IV), and platinum as a platinum catalyst. 0.2 part of a dimethylpolysiloxane having both ends dimethylvinylsiloxy group-blocked of a platinum / vinylsiloxane complex having a concentration of 1% by atomic weight 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.
It was diluted with 1 part to obtain a solution having a viscosity of 400 poise. Example 1
A PET film having a thickness of 50 μm was coated by a method similar to the method described in 1. above, but no sticky feeling was generated on the surface.

[0054]

[Chemical 7] (However, x, y, and z are x: y: z = 666: 1, respectively.
It is represented by a ratio of 00: 900, and is a number such that x + y + z = 1 and the vinyl group amount is 0.00085 mol / g. )

[Comparative Example 2] 43 parts of dimethylpolysiloxane of the above-mentioned average molecular formula (I) having a number-average degree of polymerization of 8,000 and having dimethylvinylsiloxy groups at both ends blocked, and methyl represented by the following average composition formula (VII) A mixture of 57 parts of 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. Based on 100 parts of solid content of this solution, the following average molecular formula (VII
0.1 parts of methyl hydrogen polysiloxane represented by I) and 3.3 parts of chloroplatinic acid 0.5% (platinum atom weight equivalent) isopropyl alcohol solution are mixed,
A silicone solution having a nonvolatile content of 60% was obtained.

The thickness of this is 50 μm by the same method as in the first embodiment.
A coating surface was prepared on a PET film of m. A strong adhesive surface was obtained on the surface, but it was not adhered to the film.

[0057]

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

[0058]

[Chemical 9] (Viscosity at 25 ° C 20cs)

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

This mixture was coated on 420 denier nylon 66 cloth as a fiber base material, and was heat-cured at 150 ° C. for 1 minute. The obtained coating material was uniform and the thickness of the silicone coating was 50 μm.

[0061]

[Chemical 10]

[Comparative Example 3] A dimethylpolysiloxane 1 having the average molecular formula (I) and having a viscosity at 25 ° C of 10,000 cs blocked with dimethylvinylsiloxy groups at both ends.
00 parts, 10 parts of surface-treated silica, 2.0 parts of the epoxy group-containing methylhydrogenpolysiloxane represented by the molecular formula (IX), and 2.0 parts of the organohydrogenpolysiloxane represented by the average molecular formula (IV), As a platinum catalyst, 0.2 part of a dimethylpolysiloxane solution capped with dimethylvinylsiloxy groups at both ends of a platinum / vinylsiloxane complex having a concentration of 1% based on the weight of platinum atoms was mixed to obtain 25
A mixture having a viscosity of 350 poise at 0 ° C. was obtained.

A 420 denier nylon 66 cloth was coated with this mixture as a fiber base material, and was heat-cured at 150 ° C. for 1 minute. The obtained coating material was uniform and the thickness of the silicone coating was 50 μm, but no tackiness was developed on the surface.

The adhesion and tackiness of the mixture (adhesive composition) obtained in each example were evaluated by the following methods. The results are shown in Table 1. Adhesion: PET resin or 66 nylon resin at 120 ° C /
Cured in 1 hour and left at room temperature for 1 day, then tensile strength 50
Shear adhesion was measured in mm / min. Adhesiveness: A PET film having a thickness of 50 μm or a nylon 66 cloth having a thickness of 420 denier was used as a substrate, and a roller (weight 2,000 ± 50 coated on a rubber layer having a thickness of about 6 mm) was used.
g of metal) was reciprocated once at a pressure of 300 mm / min for pressure bonding, left for one day at room temperature, and then peeled off at a speed of 300 mm / min in the 180 ° direction to measure the peeling force.

[0065]

[Table 1]

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

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C09J 7/02 JKK

Claims (1)

[Claims] 1. (A) represented by the following general composition formula (1):
100 parts by weight of organopolysiloxane, R¹ _nR² _mSiO_{(4-nm) / 2} (1) (where R is¹Is a substituted or non-aliphatic unsaturated bond
Substituted monovalent hydrocarbon group, R²Is an alkenyl group,
1.7 ≦ n ≦ 2.2, 0.0002 ≦ m ≦ 0.1, 1.
8 ≦ n + m ≦ 2.3. ) (B) Organopolish represented by the following general composition formula (2)
10-400 parts by weight of roxane, (R³ ₃SiO_1/2)_x(R³ ₂SiO )_y(SiO₂)_z (2) (where R is³Is a substituted or unsubstituted monovalent hydrocarbon group
However, a part thereof is an alkenyl group, and the alkenyl group is
0.00001 to 0. per 1 g of organopolysiloxane.
Contains 0005 moles. Also, x, y and z are respectively
0.25 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.375, 0.25
A number that satisfies ≦ z ≦ 0.667 and satisfies x + y + z = 1.
Is. ) (C) Fewer hydrogen atoms directly bonded to silicon atoms in one molecule
Organohydrogenpolysiloxane with 3
To one total alkenyl group in the components (A) and (B)
In contrast, give 0.5 to 6 hydrogen atoms bonded to silicon atoms
(D) directly bonded to silicon atom in one molecule
At least one hydrogen atom and silicon atom through the carbon atom
Epoxy group and / or trialkoxysilyl bonded to child
0.1 to 2 organosilicon compound having at least one ruthel group
0 parts by weight, (E) containing a catalytic amount of platinum or a platinum compound
A tacky adhesive composition comprising: