JPH10195151A - Silicone resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone resin compsn. improved in quick curability, depth curability, workability as an adhesive, and adhesive strength by incorporating, into the same, a modified silicone which has a specified number-average mol.wt. and is produced by polymerizing a mixture of two hydrophobic polymerizable monomers in a liq. polymer having hydrolyzable polyalkoxysilyl groups. SOLUTION: A silicone resin compsn. contg. a modified silicone having a number average mol.wt. of 5,000-30,000 and a ratio of wt. average to number average mol.wt. of 2.0-3.0 is obtd. by copolymerizing 100 pts.wt. hydrophobic polymerizable monomer which gives a homopolymer having a glass transition point of 50-150 deg.C and 20-150 pts.wt. hydrophobic polymerizable monomer which gives a homopolymer having a glass transition point of -100 to 10 deg.C. The copolymn. is conducted in a liq. polymer which has a polyether compd. as the main chain and hydrolyzable polyalkoxysilyl groups as the silicone reactive groups. The most favorable polyether compd. as the main chain of the liq. polymer is one having a polyoxypropylene structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a silicone resin composition and a method for producing the resin.

[0002]

2. Description of the Related Art Liquid polymers having a polyether compound as a main chain and having a hydrolyzable polyalkoxylyl group as a silicone reactive group are generally called modified silicones (hereinafter referred to as "modified silicones"). Modified silicone, a curing catalyst, a silane coupling agent, an inorganic filler, a viscosity improver, and, if necessary, a resin composition in which other liquid resins such as an epoxy resin and its curing agent are blended, an adhesive, a sealant, Widely used for paints, coatings, etc. In particular, in the case of adhesives and sealants, the use of one liquid can give the property of curing with atmospheric moisture at room temperature, and the cured product exhibits elasticity and flexibility without using an organic solvent. Since it maintains the fluidity that allows the coating operation, it has recently been receiving attention as a safe, convenient, and easy-to-use one-part normal-temperature, moisture-curable adhesive.

[0003] However, such a resin composition requires a long time for curing, a considerable number of days to cure to a deep part, and a strong adhesive strength due to insufficient cohesion. Therefore, while having such excellent characteristics as described above, it has been an obstacle to obtaining a wide range of applications.

[0004]

If the rapid curing property and the deep curing property, which are the drawbacks of various products using conventional modified silicones, are fundamentally improved, their usefulness will be dramatically improved. In particular, when denatured silicone is used as one solvent-free adhesive as a one-part, room-temperature, moisture-curing type, it can be used as a one-part type under the new concept of elastic bonding, and the safety of a solvent-free type. In addition to this, the addition of fast-curing and deep-curing properties (hereinafter referred to as "deep-curing") will dramatically improve the bonding process. It is even possible to bond non-porous metals such as metals that are difficult to supply moisture from. Since conventional modified silicone-based products require several hours to cure, this takes several tens of minutes, and if possible, 5 to 1
It can be cured in 0 minutes.
If curing progresses to about 50% increase in about a day, it can be said that the characteristics have been dramatically improved. In this case, if the bonding strength can be improved without losing the characteristics based on the new concept of elasticity, the reliability of bonding can be further increased.

The inventor of the present invention has utilized the present modified silicone, which has been mass-produced and stably supplied, as a raw material without relying on the structural transformation of the modified silicone, and as a raw material, the modified silicone having the above-mentioned desired properties. Tried to develop. Modified silicone is a polymer having a polyether compound as a main chain and having a polyalkoxysilyl group as a silicone reactive group, and various modification methods have been proposed to date.
Among them, techniques for polymerizing a polymerizable vinyl monomer in a modified silicone are disclosed in JP-B-63-65086, JP-B-2-44845, JP-B-2-42367, JP-B-2-35793, and JP-B-2-35793. Fairness 2-5606
No. 6, Japanese Patent Publication No. 2-52935, Japanese Patent Publication No. 3-3
No. 1,726, JP-A-7-238143, and the like. The technology described in these publications is to improve the polymer physical properties of the modified silicone,
The purpose is to improve the adhesive strength, to provide pressure-sensitive performance such as a pressure-sensitive adhesive, and to provide a function of shifting from adhesion to adhesion. However, there is no proposal in any of the above-mentioned publications regarding how to promote curing, such as imparting fast curing properties or improving deep curing properties.

[0006] In view of this situation, the present inventors have reexamined the techniques proposed so far and have been working on the development of a silicone resin having significantly improved quick-curing and deep-curing properties. I found the fact. That is, a modified polymer obtained by polymerizing a hydrophobic polymerizable monomer having a glass transition temperature of the homopolymer in the range of 50 to 150 ° C. in a modified silicone alone (hereinafter, this may be referred to as “hard monomer”) alone. Modified modification obtained by independently polymerizing a hydrophobic polymerizable monomer (hereinafter sometimes referred to as a "soft monomer") having a glass transition temperature of a modified silicone and a homopolymer thereof in a range of -100 to 10C. In any case, the quick curing property and the deep curing property of the resin composition containing the modified silicone are the same as those of the resin composition containing the modified silicone before the modification. It showed a tendency to decrease rather than sex. However, a hard monomer and a soft monomer are used together in a specific ratio, and the ratio of the number-average molecular weight and the weight-average molecular weight / number-average molecular weight of the modified silicone obtained after modification (hereinafter referred to as “dispersion degree”). Only when it is within a specific range, the resin composition containing the modified silicone is significantly improved in quick-curing property and deep-curing property, and when such a modified silicone is used as an adhesive. The adhesive strength was much better than that of the modified silicone before modification. The present invention has been completed based on such findings.

[0007]

According to the present invention, in a liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group, the homopolymer has a glass transition temperature of 50%. ~ 150 ° C
Is obtained by polymerizing a mixture of 20 to 150 parts by weight of a hydrophobic polymerizable monomer having a glass transition temperature of −100 to 10 ° C. and 100 parts by weight of a hydrophobic polymerizable monomer in the range of Molecular weight of 5000 to 30
The present invention provides a silicone resin composition containing a modified silicone having a weight average molecular weight / number average molecular weight ratio in the range of 2.0 to 3.0.

Further, according to the present invention, in a liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group, a homopolymer having a glass transition temperature of 50 to 150 ° C. A mixture of 100 parts by weight of the hydrophobic polymerizable monomer in the range and a glass transition temperature of the homopolymer of 20 to 150 parts by weight of the hydrophobic polymerizable monomer in the range of -100 to 10 ° C has a number average molecular weight of 5,000 to 5,000. 30,000 and the ratio of weight average molecular weight / number average molecular weight is 2.0 to 3.0.
And a method for producing a modified silicone characterized by obtaining a modified silicone in the range of (1).

[0009] The silicone resin composition of the present invention is capable of greatly improving fast-curing property and deep-curing property and exhibiting even more excellent adhesive strength. Therefore, the resin composition of the present invention can be suitably used in the fields of adhesives, sealants, and the like.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The modified silicone compounded in the silicone resin composition of the present invention comprises a liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group. It is produced by polymerizing a hydrophobic polymerizable monomer.

The above-mentioned liquid polymer has a polyether compound as a main chain and has at least one hydrolyzable polyalkoxysilyl group as a silicone-reactive group in a molecule. JP-B-45-36319, JP-B-46-12154, JP-B-49-32673, and JP-A-50-1
No. 56599, JP-A-51-73561 and JP-A-54-6096.

As the polyether compound, a compound having a substantially polyoxyalkylene structure has a compatibility with a polymer of a hydrophobic polymerizable monomer described below (hereinafter referred to as “hydrophobic polymer”) and a suspension stability. It is preferable because of its excellent properties, and the one having a substantially polyoxypropylene structure is most preferable because of its excellent properties.

The polyalkoxysilyl group, which is a silicone-reactive group having at least one or more in the molecule, has 1 to 3 alkoxy atoms bonded to a silicon atom and has 1 to 4 carbon atoms. A trimethoxy compound having 2 to 3 alkoxy groups and 1 carbon atom of the alkoxy group is preferably used in view of both the easiness of hydrolysis due to atmospheric moisture and the storage stability of the liquid polymer. Silyl and alkyldimethoxysilyl are preferred.
Most preferred is a methyldimethoxysilyl group among alkyldimethoxysilyl groups having good compatibility with a hydrophobic polymer and good suspension stability.

As for the molecular weight of the liquid polymer, the number average molecular weight of the modified silicone (mixture of liquid polymer and hydrophobic polymer) of the present invention is in the range of 5,000 to 30,000. Although the average molecular weight may be in the range, the modified silicone of the present invention may have a number average molecular weight of about 10,000 to 20,000 near the center of the number average molecular weight range, because it has excellent compatibility with the hydrophobic polymer and excellent suspension stability. preferable. still,
In the present invention, the molecular weight is specified by the RI method by GPC, and the number average molecular weight is a number average molecular weight in terms of polystyrene.

In the present invention, the main chain structure is substantially a polyoxypropylene structure, has two to three methyldimethoxysilyl groups as a silicone-reactive group in the molecule, and has a number average molecular weight of 10,000. Liquid polymers in the range of 20,000 to 20,000 are most preferable in terms of easy hydrolysis by moisture, compatibility with the hydrophobic polymer and suspension stability, and storage stability when the hydrophobic polymer is contained. Things.

In the present invention, in the above liquid polymer, a hydrophobic polymerizable monomer (hard polymer) 1 in which the glass transition temperature of the homopolymer is in the range of 50 to 150 ° C.
00 parts by weight and a glass transition temperature of the homopolymer of -10
A mixture of 20 to 150 parts by weight of a hydrophobic polymerizable monomer (soft monomer) in the range of 0 to 10 ° C is polymerized.

The hard monomer used in the present invention is such that when the monomer itself is homopolymerized in a liquid polymer, it becomes a suspension-dispersed appearance, and the glass transition temperature of the homopolymer is in the range of 50 to 150 ° C. It is in. Specific examples of such a hard monomer include styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene.
-Methylstyrene, 2,4-dimethylstyrene, 2,5
Styrene monomers such as dimethylstyrene, 3,4-dimethylstyrene and chlorostyrene; methacrylate monomers such as methyl methacrylate, ethyl methacrylate and tetrahydrofuran methacrylate; vinyl chloride and acrylonitrile. These hard monomers are used alone or in combination of two or more.

On the other hand, the soft monomer used in the present invention is such that when the monomer itself is homopolymerized in a liquid polymer, it is in a transparent compatible state in appearance, and the homopolymer has a glass transition temperature of -100 to 10 It is in the range of ° C. Specific examples of such a soft monomer include acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate, and vinyl ester compounds such as vinyl propionate. Examples include monomers, diene monomers such as butadiene, isoprene, and chloroprene. These soft monomers are
One type is used alone, or two or more types are used in combination.

When the hard monomer and the soft monomer are copolymerized, styrene and styrene are used as the hard monomer.
Selecting at least one selected from the group consisting of methyl methacrylate and tetrahydrofuran methacrylate,
Further, as a soft monomer, the alkyl group has 2 to 2 carbon atoms.
When an alkyl acrylate in the range of 0 is selected, the resulting modified silicone is excellent in compatibility and suspension stability. Also, no change with time such as thickening and separation is observed, which is preferable. In particular, at least one selected from the group consisting of methyl methacrylate and tetrahydrofuran methacrylate as a hard monomer, and at least one selected from the group consisting of ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate as a soft monomer Is most preferable because, in addition to the above-mentioned effects, the modified silicone obtained is particularly excellent in adhesiveness such as adhesive strength.

In the present invention, the ratio of the hard monomer to the soft monomer is 20 to 150 parts by weight per 100 parts by weight of the former. 20 soft monomers
In both the case where the amount is less than 150 parts by weight and the case where the amount is less than 150 parts by weight, the rapid curing property and the deep curing property are not improved, and the resulting resin composition containing the modified silicone is poor in adhesive strength, The desired modified silicone cannot be produced. In the present invention, in particular, 30 to 100 soft monomers are used per 100 parts by weight of the hard monomers.
It is preferred to use parts by weight.

Further, in the present invention, it is necessary to add 10 to 100 parts by weight of a hydrophobic polymerizable monomer (hard monomer and soft monomer) per 100 parts by weight of the liquid polymer. If the ratio is outside this range, it becomes difficult to obtain a modified silicone having improved fast curability and deep curability. In the present invention, it is desirable to add 20 to 50 parts by weight of a hydrophobic polymerizable monomer per 100 parts by weight of the liquid polymer.

In polymerizing a mixture of a hard monomer and a soft monomer at a specific ratio in a liquid polymer, known methods can be widely applied, for example, a method disclosed in Japanese Patent Publication No. 63-65086 can be easily used. Can be done. As a typical method, there is a method in which a modified silicone is charged in a kettle in advance, and a mixed solution or dispersion of a polymerizable monomer, an initiator, a chain transfer agent and the like is continuously dropped to carry out polymerization. This polymerization may be carried out by selecting a usual polymerization method, but as a simple method, a method using a radical initiator, a peroxide such as benzoyl peroxide, azobisisobutyronitrile as an initiator. Known radical polymerization initiators such as azo compounds and persulfates may be used. When conducting polymerization in this usual way, a chain transfer agent can be used to adjust the number average molecular weight and the degree of dispersion of the mixture. The type and amount of the chain transfer agent are not particularly limited, but non-silicone compounds such as mercaptans and halogen-containing compounds that are generally used frequently are preferable. In the chain transfer agent, since the object of the present invention is a solventless adhesive, a long-chain alkyl-based mercaptan such as lauryl mercaptan, which is hardly volatilized, can be obtained, rather than a highly volatile one. The modified silicone is preferably used in an appropriate amount such that the molecular weight falls within the molecular weight range of the present invention.

When the above-mentioned hard monomer, soft monomer, initiator and chain transfer agent contain a silicone-reactive group, the resulting modified modified silicone tends to have a low curability and a deep curability. Therefore, it is desirable that the hard monomer, soft monomer, initiator and chain transfer agent used in the present invention do not contain a silicone-reactive group.

In the above polymerization method, addition of the hydrophobic polymerizable monomer in the liquid polymer may be carried out as it is, so that there is no need to remove the organic solvent in order to obtain a solventless adhesive or the like. Since both the compatibilization and suspension can be promoted by the heat of polymerization when the polymer of the hydrophobic polymerizable monomer is formed in the liquid polymer, the above method can be said to be an excellent method.

The hard monomer and the soft monomer, which are the hydrophobic polymerizable monomers, are used by mixing them from the beginning of the polymerization, or in a stepwise manner in which one of the monomers is polymerized first while the other is polymerized. However, it is better to mix a hard monomer and a soft monomer from the beginning of the polymerization and copolymerize. This is preferable because it gives a sense of transparency, enhances the initial tack, and further improves the quick curability.

The modified silicone thus obtained has a number average molecular weight in the range of 5,000 to 30,000 and a dispersity in the range of 2.0 to 3.0. If the number average molecular weight of the modified silicone is less than 5000, the viscosity will be low, but the adhesive strength will be reduced due to the decrease in cohesive strength, and the desired fast curability will not be obtained. On the other hand, when the number average molecular weight is more than 30,000, it is difficult to maintain a liquid having a high viscosity, and although the rapid curability is somewhat improved, the deep curability is only about the same as that of the modified silicone before modification. Further, if the degree of dispersion is less than 2.0, the initial tack is reduced, so that the rise of the initial adhesion is delayed,
Conversely, when the degree of dispersion is greater than 3.0, the deep curability decreases, and in any case, inconvenience occurs. The modified silicone of the present invention has a number average molecular weight of 10,000 to 2,000.
Those having a range of 0 and a dispersity of 2.0 to 2.5 are preferred.

The silicone resin composition of the present invention contains the modified silicone described above. In the present invention, the composition containing the modified silicone obtained by the above polymerization method can be used as it is as the resin composition of the present invention. In 100 parts by weight of the silicone resin composition of the present invention, the above modified silicone is usually contained in an amount of about 90 to 100.
It is good to be contained by weight, preferably 95 to 99 parts by weight.

A curing catalyst can be added to the silicone resin composition of the present invention in order to promote curing with moisture. As the curing catalyst, a conventionally known silanol condensation catalyst (curing catalyst) can be widely used. Specific examples thereof include titanium esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxyls such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate, and tin ferzaticate. Acid salts; a reaction product of dibutyltin code oxide and a phthalate; dibutyltin diacetylacetonate;
Organic aluminum compounds such as aluminum triacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate;
Chelate compounds such as titanium tetraacetylacetonate; lead octylate; iron naphthenate; bismuth compounds such as bismuth-tris (neodecanoate) and bismuth-tris (2-ethylhexoate). These catalysts may be used alone or in combination of two or more. Further, a known amine catalyst such as laurylamine may be used. The blending amount of the curing catalyst is not particularly limited, but it is generally preferable to blend the curing catalyst in an amount of about 0.1 to 10 parts by weight in 100 parts by weight of the silicone resin composition of the present invention.

Further, the silicone resin composition of the present invention contains vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and N-β (aminoethyl)-in order to improve adhesion and storage stability. A silane coupling agent such as γ-aminopropyltrimethoxysilane can be blended. The blending amount of the silane coupling agent is not particularly limited, but it is generally preferable to blend the silane coupling agent in an amount of about 0.1 to 15 parts by weight based on 100 parts by weight of the silicone resin composition of the present invention.

The silicone resin composition of the present invention may further contain, if necessary, a filler, a plasticizer, a viscosity improver, and other additives.

As the filler, a known filler can be used.
Specifically, fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black,
Calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite,
Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and glass balloons, and fibrous fillers such as asbestos, glass fibers and filaments can be used.

As the plasticizer, known plasticizers can be used, and specifically, phthalate esters such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate;
Aliphatic carboxylic esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate and butyl oleate; glycol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxidized soybean oil , Epoxy plasticizers such as benzyl stearate; chlorinated paraffins and the like can be used alone or in a mixture of two or more. In addition, polyoxypropylene monol, polyoxypropylene diol, and a terminal-modified product thereof can also be used. Examples of the terminal modified product include a compound in which a terminal hydroxyl group is modified to an alkoxy group or an alkenyloxy group, a compound blocked by a hydrocarbon group via a urethane bond, an ester bond, a urea bond, or a carbonate bond.

Examples of the viscosity improver include fatty acid amidates such as amide wax.

Further, as other additives, for example, pigments, various antioxidants, ultraviolet absorbers and the like can be used.

[0035]

The present invention will be further clarified with reference to the following examples. In the following, “parts” means “parts by weight”, and “%” means “% by weight”.

First, an example of the synthesis of the modified silicone will be described.

Reference Example 1 A commercially available modified silicone (Kaneka MS Polymer S30) having a main chain structure of polyoxypropylene and having about three methyldimethoxysilyl groups as silicone reactive groups in the molecule.
3. Design molecular weight 10,000, viscosity 200 Pa · s / 2
GPC (RI meter, polystyrene gel 100Å, 500Å, 103Å, 104Å (four in series), elution solvent tetrahydrofuran, flow rate 1.0 ml, 3 ° C., manufactured by Kanegafuchi Chemical Industry Co., Ltd.)
/ Min, column temperature 40 ° C., manufactured by Waters Limited), the number average molecular weight (hereinafter abbreviated as “Mn”) = 13,000 in terms of polystyrene, and the weight average molecular weight (hereinafter abbreviated as “Mw”) = 22000. , The degree of dispersion (M
(w / Mn) = 1.69, moisture 50 ppm, evaporation residue 9
The water absorption was 9.5% and the water absorption was 140 mg / 100 g.
In addition, about 1 g of each modified silicone was precisely weighed on an aluminum dish, and the evaporation residue was calculated from the remaining amount after being left at 150 ° C. for 1 hour. About 100 g of each modified silicone was precisely weighed in a pudding cup, and the increased amount of water absorbed after standing for 24 hours in an environment at 23 ° C. and a relative humidity of 50% was defined as the amount of water absorption. This modified silicone is referred to as “modified silicone A”.

Example 1 A stirrer, a dropping funnel, a reflux tube, a thermometer, a nitrogen gas flow device,
1000 parts of the modified silicone A was charged into a 2-liter four-neck separable flask equipped with a decompression device, and the temperature was adjusted to 90 ° C. while stirring under a nitrogen stream. Methyl methacrylate (hereinafter abbreviated as “MMA”) 2 as a hard monomer in advance
A mixture of 00 parts and 200 parts of butyl acrylate (hereinafter abbreviated as “BA”) as a soft monomer, 4 parts of azobisisobutyronitrile (hereinafter abbreviated as “AIBN”) as an initiator, and lauryl mercaptan (hereinafter abbreviated as “AIBN”) as a chain transfer agent. (Hereinafter abbreviated as "LM"), 6 parts of the polymerizable monomer mixed solution added and dissolved was transferred to a dropping funnel, and reacted at a reaction temperature of 90-10.
Dropping was performed at 0 ° C. over 3 hours to perform radical polymerization. Further aging at 100 ° C. for 3 hours to reduce unreacted monomers, vacuum distillation at 10 to 20 mmHg for 1 hour at the same temperature to remove unreacted monomers, cooling and taking out The modified silicone resin composition of the invention was obtained. This mixture was a viscous liquid slightly emulsified in appearance, having a viscosity of 430 Pa · s / 23 ° C. and an evaporation residue of 98.8.
%, Water content 40 ppm, and water absorption 80 mg / 100 g. The molecular weight was measured by GPC in the same manner as in Reference Example 1. As a result, Mn was 15,000 and the degree of dispersion was 2.20. This composition is referred to as “modified silicone B”.

Example 2 In the same manner as in Example 1, radical polymerization was carried out using modified silicone A as a matrix while changing only the combination amount of a hard monomer and a soft monomer. That is, the first embodiment
The difference is that a mixed monomer of 100 parts of BA with respect to 300 parts of MMA is used, and the amount of the initiator, the amount of the chain transfer agent and the total amount of the mixed monomer with respect to the matrix are the same as in Example 1. The appearance of the modified silicone resin composition of the present invention obtained by the same operation and method as in Example 1 is a viscous liquid having a higher whiteness than that of Example 1, and having a viscosity of 480 Pa · s / 23.
° C, evaporation residue 98.5%, water content 50 ppm, water absorption 8
It was 0 mg / 100 g. Also, as in Reference Example 1, GP
When the molecular weight was measured by C, Mn = 1500
0 and the degree of dispersion = 2.24. This composition is referred to as “modified silicone C”.

Comparative Example 1 In the same manner as in Example 1, radical polymerization was carried out using modified silicone A as a matrix while changing only the combination amount of a hard monomer and a soft monomer. That is, the first embodiment
The difference is that the mixed monomer of 50 parts of BA is used for 350 parts of MMA, and the amount of the initiator, the amount of the chain transfer agent and the total amount of the mixed monomer with respect to the matrix are the same as in Example 1. The appearance of this modified silicone resin composition obtained by the same operation and method as in Example 1 is a viscous liquid having a significantly higher whiteness than that of Example 1, having a viscosity of 630 Pa · s / 23 ° C. and an evaporation residue of 98. 5%, water content 50ppm, water absorption 90mg
/ 100 g. The molecular weight was measured by GPC in the same manner as in Reference Example 1. As a result, Mn was 16,000 and the degree of dispersion was 2.38. This composition is referred to as “modified silicone D”.

Comparative Example 2 In the same manner as in Example 1, radical polymerization was carried out using modified silicone A as a matrix while changing only the combination amount of a hard monomer and a soft monomer. That is, the first embodiment
The difference is that a mixed monomer of 300 parts of BA per 100 parts of MMA is used, and the amount of the initiator, the amount of the chain transfer agent and the total amount of the mixed monomer with respect to the matrix are the same as in Example 1. The appearance of this modified silicone resin composition obtained by the same operation and method as in Example 1 is a slightly emulsified viscous liquid, a viscosity of 220 Pa · s / 23 ° C., and an evaporation residue of 98.6.
%, Water content 40 ppm, water absorption 70 mg / 100 g. When the molecular weight was measured by GPC in the same manner as in Reference Example 1, Mn was 18,000 and the degree of dispersion was 2.35. This composition is referred to as “modified silicone E”.

Comparative Example 3 In the same manner as in Example 1, radical polymerization was carried out using modified silicone A as a matrix while changing only the amount of the chain transfer agent as a polymerization degree regulator. That is, the difference from Example 1 is that the amount of lauryl mercaptan was 0.5 part, and the ratio of the mixed monomers, the total amount thereof, and the amount of initiator were the same as in Example 1. The appearance of the modified silicone resin composition obtained by the same operation and method as in Example 1 was in the same milky state as in Example 1, but was more viscous and had a viscosity of 1300P.
a · s / 23 ° C, evaporation residue 99.0%, water content 40pp
m, and the water absorption was 75 mg / 100 g. Reference Example 1
When the molecular weight was measured by GPC in the same manner as in
= 45000 and the degree of dispersion = 3.14. This composition is referred to as “modified silicone F”.

Comparative Example 4 A radical polymerization was carried out in the same manner as in Example 1, except that the amount of the chain transfer agent as a polymerization regulator was changed, and the modified silicone A was used as a matrix. That is, the difference from Example 1 is that the amount of lauryl mercaptan was set to 20 parts, and the mixed monomer ratio, the total amount thereof, and the amount of initiator were the same as in Example 1. The appearance of this modified silicone resin composition obtained by the same operation and method as in Example 1 was a transparent viscous liquid, a viscosity of 180 Pa · s / 23 ° C., an evaporation residue of 97.3%, a water content of 50 ppm, and a water absorption of 60 mg. / 100 g. When the molecular weight was measured by GPC in the same manner as in Reference Example 1, Mn was 4000 and the degree of dispersion was 1.86. This composition is referred to as “modified silicone G”.

Reference Example 1, Examples 1-2 and Comparative Examples 1-4
Table 1 summarizes the measurement results of the composition, properties and molecular weight of

[0045]

[Table 1]

From the above results, the modified silicone A (Example 1), the modified silicone C (Example 2) obtained by polymerizing a hydrophobic monomer were compared with the water absorption of the modified silicone A (Reference Example 1) having high hydrophilicity. The modified silicone D (Comparative Example 1), the modified silicone E (Comparative Example 2), the modified silicone F (Comparative Example 3), and the modified silicone G (Comparative Example 4) all have the same reduction in water absorption. I understood.

Using the modified silicone obtained by the above method,
Using a 2 liter planetary mixer (manufactured by Inoue Seisakusho), 300 parts of heavy calcium carbonate from which water was removed by heating and drying per 1000 parts of each modified silicone A to G, curing catalyst (dibutyltin dilaurate) 5
0 parts, aminosilane (N-β (aminoethyl) -γ-aminopropyltrimethoxysilane) as an adhesion-imparting agent
20 parts and 50 parts of dioctyl adipate as a diluent were mixed to obtain respective adhesives. For example, the adhesive using the modified silicone B is referred to as a modified silicone adhesive B, and the modified silicones A to G and the modified silicone adhesive A
G correspond.

Using these adhesives, the respective effects were confirmed by the following methods.

(I) Measurement of sticking time: An aluminum plate of 300 mm square (thickness 3 mm) was cut into an aluminum plate of 25 mm square (thickness 10 mm) in an atmosphere of 23 ° C. and a relative humidity of 50%. Each adhesive was applied so that the thickness of the adhesive layer was about 0.2 mm, and the wood pieces were pressed on an aluminum plate to measure how long it could be fixed. The measurement was performed every two minutes, and the time when the finger was not easily moved by moving with a finger was defined as the fixing time.

(Ii) Measurement of rise time of initial adhesive strength: The thickness of each adhesive was reduced to about 0.1 mm by a bar coater on a 300 mm square plywood in an atmosphere of 23 ° C. and 50% relative humidity. A polyester transparent film (thickness: 50 μm) immediately subjected to corona discharge treatment was laminated and pressed with a rubber roll, and the film was applied to the film.
A cut having a width of mm was made, and the peel strength was measured over time using a spring balance. The median value near the center was read as the peel strength. The maximum strength is 2kg
-The time when f exceeded was defined as the end point, and the time was recorded.

(Iii) Measurement of tensile shear bond strength after 30 minutes: length 100 in an atmosphere of 23 ° C. and 50% relative humidity.
Asada materials (wood) with a width of 25 mm, a width of 25 mm and a thickness of 5 mm are applied to each other so that the adhesive area is 25 mm × 25 mm and the adhesive layer is about 0.2 mm, and are immediately superimposed and adhered. For 30 minutes, and its tensile shear bond strength was measured. Tensile speed at the time of measurement is 5m
m / min, and the number of test pieces was 5, and the average value of the maximum adhesive strengths of each test piece was defined as the adhesive strength. The test equipment used was Autograph AG5000 (manufactured by Shimadzu Corporation) (unit: N / c)
m ² ). (Iv) Measurement of Deep Curability: Each adhesive was mixed in a 50 cc PP pudding cup in an atmosphere of 23 ° C. and 50% relative humidity so as to be heaped, and the surface was homogenized with a putty knife. The specimen was scraped off. Twenty-four hours later, the cured portion of the surface layer was peeled off so as to peel off the skin, and the uncured adhered portion was wiped off. The thickness was measured at five points with a vernier caliper, and the average value was defined as the degree of deep curing (unit: mm) ).

(V) Measurement of tensile shear adhesive strength for judging internal curability: adhesion between aluminum plates having a width of 25 mm, a length of 100 mm and a thickness of 3 mm in an atmosphere of 23 ° C. and 50% relative humidity. The area is 25mm x 25mm,
Immediately after applying a thick coat of the adhesive layer to a thickness of 5 mm using a spacer, one aluminum plate is overlapped and brought into close contact, and left under the same conditions for 7 days. Measurement of the tensile shear bond strength and internal curing The extent of the condition was observed. The tensile speed at the time of measurement was 5 mm / min, the number of test pieces was 5, and the average value of the respective maximum adhesive strengths was taken as the adhesive strength. The average value was shown. However, if the cured state was already obtained, it was described as complete curing. Test equipment is Autograph AG500
0 (manufactured by Shimadzu Corporation) was used (unit: N / cm ² , the cured state was visually determined as the area% of the uncured state, and expressed as an average).

(Vi) Measurement of tensile shear bond strength of various materials: 25 m width in an atmosphere of 23 ° C. and 50% relative humidity.
m, length 100 mm, thickness 3 mm aluminum plate (denoted as “aluminum”), rigid polyvinyl chloride plate (PVC
) And a polycarbonate plate (described as “Polyka”) were adhered to each other. The bonding area is 25mm x 25mm,
Each adhesive was applied to one side so that the adhesive layer was about 0.2 mm, and about 30 seconds after the application, one of the test pieces was overlapped and adhered to each other, and allowed to stand for 7 days under the same conditions. Was measured. The tensile speed at the time of measurement was 5 mm / min,
The number of test pieces was 5, and the average value of the respective maximum adhesive strengths was defined as the adhesive strength. Test equipment is Autograph AG500
0 (manufactured by Shimadzu Corporation) was used (unit: N / cm ² ).

[0054]

[Table 2]

Thus, the modified silicone-containing adhesives obtained in Examples 1 and 2 were modified adhesives containing the modified silicone used in the matrix (Reference Example 1) and the modified silicones of Comparative Examples 1 to 4, respectively. As compared with any of the above adhesives, the initial adhesive strength was rapidly developed, the curing was advanced to the deep part and inside, and the adhesive strength by various materials was excellent.

Example 3 In the same manner as in Example 1, a hard monomer was polymerized first, and then a soft monomer was polymerized. That is, 1000 parts of the modified silicone A was charged, and M was used as a hard monomer.
A monomer mixture composed of 200 parts of MA, 2 parts of AIBN and 3 parts of LM was dropped at a reaction temperature of 90 to 100 ° C. over 1 hour and 30 minutes, and 200 parts of BA, 2 parts of AIBN and 3 parts of LM were immediately prepared as a soft monomer prepared in advance. Was subjected to radical polymerization at the same temperature and at the same time, and was aged, distilled under reduced pressure, and cooled in the same manner as in Example 1, and was taken out. This mixture is a viscous liquid having slightly higher whiteness than that of Example 1, having a viscosity of 470 Pa · s / 23 ° C., an evaporation residue of 98.6%, a water content of 50 ppm, and a water absorption of 75 mg / 10
It was 0 g. When the molecular weight was measured in the same manner as in Reference Example 1, Mn = 13000 and the degree of dispersion = 2.15.
Met.

This composition is referred to as “modified silicone H”
An adhesive containing a curing catalyst or the like in the same manner as described above is referred to as “modified silicone adhesive H”.

Example 4 In the same manner as in Example 1, a soft monomer was polymerized first, and then a hard monomer was polymerized. The only difference from Example 3 was that the order of dropping the hard monomer and the soft monomer was changed, and in the same manner as in Example 3, a viscous liquid having a slightly higher transparency than that of Example 1 and a viscosity of 560 Pa ·
s / 23 ° C., evaporation residue 99.2%, water content 50 ppm,
The water absorption was 60 mg / 100 g. When the molecular weight was measured in the same manner as in Reference Example 1, Mn = 1800
0 and the degree of dispersion was 2.45.

This composition is referred to as “modified silicone I”,
An adhesive containing a curing catalyst and the like in the same manner as above is referred to as “modified silicone adhesive I”.

In addition, in addition to Example 1 to Examples 3 and 4, in order to make it easier to understand the difference in polymerization method, properties and measurement results of molecular weight, the results are shown in Table 3 below.

[0061]

[Table 3]

Next, the same test as described above was conducted by comparing the modified silicone adhesive H and the modified silicone adhesive J obtained by processing each modified silicone into an adhesive. Table 4 shows the results.

[0063]

[Table 4]

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Claims (8)

[Claims] 1. A liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group, wherein a homopolymer has a glass transition temperature of 50 to 150 ° C. The glass transition temperature of 100 parts by weight of the reactive monomer and the homopolymer is −
Hydrophobic polymerizable monomer 20 in the range of 100 to 10 ° C.
A modified silicone having a number average molecular weight in the range of 5,000 to 30,000 and a weight average molecular weight / number average molecular weight ratio in the range of 2.0 to 3.0 is obtained by polymerizing a mixture of about 150 parts by weight. Silicone resin composition. 2. A compounding amount of a hydrophobic polymerizable monomer per 100 parts by weight of a liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group, based on the total amount of the hydrophobic polymerizable monomer. 10
The modified silicone resin composition according to claim 1, wherein the amount is from 100 to 100 parts by weight. 3. The glass transition temperature of the homopolymer is from 50 to 50.
The hydrophobic polymerizable monomer in the range of 150 ° C. is at least one selected from the group consisting of styrene, methyl methacrylate and tetrahydrofuran methacrylate, and the glass transition temperature of the homopolymer is −100 to 10 ° C.
The modified silicone resin composition according to claim 1 or 2, wherein the hydrophobic polymerizable monomer in the range of (1) is an alkyl acrylate having an alkyl group having a carbon number of 2 to 20. 4. A liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group, wherein a homopolymer has a glass transition temperature in the range of 50 to 150 ° C. The glass transition temperature of 100 parts by weight of the reactive monomer and the homopolymer is −
Hydrophobic polymerizable monomer 20 in the range of 100 to 10 ° C.
~ 150 parts by weight of the mixture was polymerized to give a number average molecular weight of 5
000-30000 and weight average molecular weight /
A method for producing a modified silicone, wherein a modified silicone having a number average molecular weight ratio in the range of 2.0 to 3.0 is obtained. 5. A hydrophobic polymerizable monomer is added in an amount of 10 to 100 per 100 parts by weight of a liquid polymer having a polyether compound as a main chain and having a hydrolyzable polyalkoxysilyl group as a silicone-reactive group.
The method for producing a modified silicone according to claim 4, which is blended by weight. 6. The glass transition temperature of the homopolymer is 50 to 50.
The hydrophobic polymerizable monomer in the range of 150 ° C. is at least one selected from the group consisting of styrene, methyl methacrylate and tetrahydrofuran methacrylate, and the glass transition temperature of the homopolymer is −100 to 10 ° C.
The method for producing a modified silicone according to claim 4 or 5, wherein the hydrophobic polymerizable monomer in the range of (1) is an alkyl acrylate having an alkyl group having a carbon number of 2 to 20. 7. The glass transition temperature of the homopolymer is 50 to 50.
The polymerization is carried out by mixing a hydrophobic polymerizable monomer in the range of 150 ° C and a hydrophobic polymerizable monomer having a glass transition temperature of the homopolymer in the range of -100 to 10 ° C in the initial stage of the polymerization. Item 5. The method for producing a modified silicone according to Item 4. 8. The method for producing a modified silicone according to claim 4, wherein the polymerization includes a polymerizable monomer, an initiator, and a polymerization degree regulator having no silicone-reactive group in the reaction system.