JPH0242398B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] The present invention relates to a substantially solvent-free adhesive composition using a polyether having at least one hydrolyzable silicon group. [Prior Art] At present, adhesives are generally used in the form of pressure-sensitive tapes or sheets applied to cloth, paper, plastic films, etc. for stationery, medical, masking, protection, and other purposes. Conventionally, solvent-based adhesives such as natural rubber and synthetic rubber have been used as pressure-sensitive adhesives, but because they use organic solvents, they pose problems such as bad odors, fire hazards, occupational safety and health concerns, and pollution. Due to the above problems, there is a strong demand for solvent-free adhesives in the adhesive tape industry. On the other hand, in recent years, acrylic ester copolymer emulsions have been used as solvent-free adhesives because they are water-based and have better aging resistance and coloring resistance than synthetic rubber-based adhesives. It has a characteristic bad odor of acrylic acid, and is not completely satisfactory. The inventors of the present invention conducted intensive research to solve the above problems, and found that by using a polyether having at least one hydrolyzable silicon group at the end, a solvent-free adhesive with no bad odor was created. The inventors have discovered that it is possible to obtain a drug composition, and have arrived at the present invention. [Configuration of the Invention] That is, the present invention contains at least one hydrolyzable silicon group, and the main chain essentially has the formula -R-O-(R
has chemically bonded repeating units represented by a divalent alkylene group) and has a molecular weight of 300 to 15,000.The tackifying resin is 10 to 100 parts by weight per 100 parts by weight of polyether. The gist is an adhesive composition characterized by the following: The polyether containing at least one hydrolyzable silicon group as used in the present invention must contain at least one hydrolyzable silicon group at the end of the molecule or in the side chain. The hydrolyzable silicon group has the general formula (In the formula, R ² is a monovalent hydrocarbon group having 1 to 12 carbon atoms selected from alkyl groups and aryl groups, X is a hydride group, halogen group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group) (a is an integer of 0, 1 or 2) may be arbitrarily used. The hydrolyzable silicon group can be present in the main chain and/or at the terminal end of the polyether, but from the viewpoint of production, it is preferable to introduce it essentially at the terminal end. The backbone of the polyether used is essentially of the formula -
R ¹ -O- (here, R ¹ is a divalent organic group,
It is most effective when most of the groups are hydrocarbon groups having 1 to 4 carbon atoms. Specifically, R ¹ is -CH ₂ -, -CH ₂ CH ₂ -,

【formula】

[Formula] ―CH ₂ CH ₂ CH ₂ CH ₂ ―,

[Formula] etc. Polyethers consisting of only one type of repeating unit or two or more types of repeating units are effectively used. especially

[Examples and effects]

Examples will be specifically described below, but the present invention is not limited thereto. Reference example 1 Polyoxypropylene glycol with an average molecular weight of 3200 (allyl ether groups account for 15% of all end groups,
3% propenyl ether group, 82% hydroxyl group
Transfer 320 g of the mixture into a pressure-resistant reaction vessel equipped with a stirrer and purged with nitrogen. Subsequently, after adding 40.8 g of powdered caustic soda (purity 98%), the temperature was raised to 60°C.
After this, add 7.76g of bromochloromethane and heat at 60°C.
Perform the reaction for 10 hours. Next, the temperature of the reaction system is
Lower the temperature to 50℃, add 9.2g of allyl chloride, and 50℃
Perform the reaction for 10 hours. After the reaction is complete, the contents are taken out into a beaker, diluted with 1000 g of normal hexane, and treated with 50 g of aluminum silicate under stirring at room temperature for 1 hour. The strained cake is then washed several times with n-hexane. The average molecular weight is 8000 by removing volatiles from the liquid by distillation.
300 g of propylene oxide polymer was obtained.
The terminal group of the polymer is an allyl ether group90
%, propenyl ether groups 8%, and hydroxyl groups 2%. Place 84 g of the obtained polymer in a 500 ml pressure-resistant reaction vessel equipped with a stirrer. Catalyst solution of chloroplatinic acid (solution of H ₂ PtCl _{6.6H 2} O2 g dissolved in 20 ml of isopropanol and 788 ml of tetrahydrofuran)
Add 0.05ml and 1.6g of methyldimethoxysilane,
After reacting at 100℃ for 8 hours, 70% of the end groups were removed by removing the volatiles.

An alkylene oxide polymer having the formula [Formula] is obtained. Reference Example 2 The reaction was carried out in the same manner as in Reference Example 1, except that the amount of methyldimethoxysilane used was 1.3 g, and 55% of the terminal groups were
but

An alkylene oxide polymer having the formula [Formula] was obtained. Reference Example 3 The reaction was carried out in the same manner as Reference Example 1 except that 2.7 g of triethoxysilane was used instead of methyldimethoxysilane, and 75% of the terminal groups were (CH ₃ CH ₂ O) -
An alkylene oxide polymer having a ₃ SiCH ₂ CH ₂ CH ₂ —O— group was obtained. Example 1 Alkylene oxide polymer obtained in Reference Example 1
100 parts by weight of rosin ester resin (softening point 95℃,
90 parts by weight of KOH (acid value 14 mg/g) were added and mixed uniformly. 2.0 parts by weight of dibutyltin phthalate was added and mixed to obtain an adhesive composition. Apply 0.06% of this composition to kraft paper with paraffin treatment on the back side.
After coating to a thickness of mm, the tape was cured at 50°C for 12 hours to prepare an adhesive tape, and its adhesion to a stainless steel plate and Dow rolling tack were measured according to JIS-Z-1523. The results are shown in Table 1. Example 2 Alkylene oxide polymer obtained in Reference Example 2
20 parts by weight of _C5 petroleum resin (softening point 100℃)
An adhesive tape was obtained in the same manner as in Example 1 except that parts by weight were used. The same measurements as in Example 1 were performed on this adhesive tape, and the results shown in Table 1 were obtained. Example 3 Alkylene oxide polymer obtained in Reference Example 3
100 parts by weight of hydrogenated rosin ester resin (softening point 100
℃, 60 parts by weight of oxidized 18KOH mg/g) was added and mixed uniformly. Thereafter, an adhesive tape was obtained in the same manner as in Example 1. The same measurements as in Example 1 were performed on this adhesive tape, and the results shown in Table 1 were obtained. Comparative Example 1 In Example 1, the rosin ester resin was
An adhesive tape was prepared in the same manner as in Example 1 except that parts by weight were used, but the adhesive layer had poor cohesive force.
After bonding to a stainless steel plate as an adherend, when peeled off, adhesive remained on the surface of the stainless steel plate.

【table】

Claims (1)

[Claims] 1. A chemically bonded compound containing at least one hydrolyzable silicon group and having a main chain essentially represented by the formula -R ¹ -O- (R ¹ is a divalent alkylene group). having a repeating unit with a molecular weight of
1. A pressure-sensitive adhesive composition characterized in that 10 to 100 parts by weight of a tackifying resin is blended to 100 parts by weight of a polyether having a molecular weight of 300 to 15,000. 2. A patent claim in which the hydrolyzable silicon group is at least one type selected from a hydride group, a halogen group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminoxy group, and a mercapto group bonded to a silicon atom. The pressure-sensitive adhesive composition according to scope 1. 3 The hydrolyzable silicon group has the formula (In the formula, R ² is a monovalent hydrocarbon group having 1 to 12 carbon atoms selected from alkyl groups and aryl groups, X is a hydride group, halogen group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group) 2. The pressure-sensitive adhesive composition according to claim 1, wherein the adhesive composition is a group selected from a group consisting of a group consisting of a group selected from a group consisting of a group consisting of a group consisting of an aminooxy group, an aminooxy group, and a mercapto group, and a being an integer of 0, 1, or 2. 4. The pressure-sensitive adhesive composition according to claim 3, wherein X- is an alkoxy group. 5. The adhesive composition according to claim 1, wherein the tackifier resin is a rosin or a petroleum resin.