JPS587471A - Preparation of pressure-sensitive adhesive material - Google Patents

Abstract

PURPOSE:To prevent the sticking and adhesion of an pressure-sensitive adhesive material to rolls without adversely affecting the adhesive force of the adhesive material in preparing a polyurethane pressure-sensitive adhesive material, by treating the adhesive layer surface before the completion of the curing reaction with water. CONSTITUTION:A composition 1 prepared by incorporating (A) an active hydroxyl group-containg compound, e.g. ethylene glycol, with (B) a bituminous material, e.g. straight asphalt, a tackifier resin, e.g. alkyl phenolic resin, and an assistant as a tackifier material, and (C) a polyisocyanate compound is applied and cast onto the top of a support 2, and the surface thereof is treated with water (B) before the completion of the curing reaction (A) (40-100 deg.C) to give the aimed adhesive material 4. The equivalent raio between the components (A) and (C) is preferably 1:(0.4-0.95). USE:A preparation of the titled material aiming at the bonding, packaging, insulation, anticorrosion, vibration damping, etc.

Description

[Detailed Description of the Invention] The present invention is pressure sensitive! ! ! The present invention relates to a manufacturing method for adhesive materials, and more particularly to a manufacturing method that makes it possible to obtain a urethane-based pressure-sensitive adhesive material having excellent adhesion to various adherends in a shortened process.

Conventionally, methods for manufacturing pressure-sensitive adhesive materials used for purposes such as adhesion, packaging, insulation, anti-corrosion, and vibration damping include (1)
A plastic sheet is a solvent-based adhesive composition made by dissolving a mixture of a rubber-based or acrylic-based polymer material, a tackifying resin, a softener, a degradable agent, etc. in an organic solvent to form a solution with a solid content of approximately 50%. Coat it on a support such as
There is a method in which the solvent is volatilized in a subsequent heating and drying step to form an adhesive layer on the support, and then a release paper is layered and rolled up. However, the solvent used in this method does not contribute to its function as an adhesive and must be used in a large amount relative to the solid content, so it requires a device to volatilize the solvent, a heat source, etc.
Furthermore, there are drawbacks such as the need for a device for recovering the solvent.

In order to improve these drawbacks, a method has been proposed in which a polyurethane adhesive composition containing a tackifying resin, that is, a solvent-free adhesive composition is used.

However, this manufacturing method requires a step of applying the adhesive composition onto the support and then passing it through a heated hardening oven for the curing reaction of the adhesive layer. Moreover, in this process, the adhesive layer is sticky, so it cannot be used as a roll.
This method inevitably requires long linear equipment, which has drawbacks such as high equipment costs and a large floor space. In order to solve this problem, it may be possible to manufacture ima and i on the adhesive layer while uncured through a process using overlapping rolls, but this may result in poor adhesion to the release paper and the thickness of the adhesive layer. If the adhesive is relatively thick, the release paper may fold when passing through the P-sil, causing wrinkles on the surface of the adhesive layer and deteriorating the quality.

Furthermore, the adhesive strength of polyurethane-based adhesive materials obtained by conventional methods is not necessarily sufficient, and there are limits to public funding for their use.

As a result of extensive research in order to solve the problems of these conventional techniques, the fjA authors of the present invention discovered that the I! 'We have discovered that it is possible to prevent adhesion to the roll by treating the surface of the adhesive layer with water. Moreover, this water treatment not only has no negative effect on the adhesive strength of the pressure-sensitive adhesive material, but also
In fact, it was found that the adhesive strength was significantly improved. The present invention was completed based on these findings.

That is, the present invention provides (4) an active hydrogen group-containing compound;
In the production of a pressure-sensitive adhesive material in which an adhesive layer made of an adhesive composition comprising a tackifying substance and a (0)l-lysocyanate compound is formed under a support, the surface of the adhesive layer is soaked with water before the curing reaction is completed. The present invention provides a method for producing a pressure-sensitive adhesive material, which is characterized in that the pressure-sensitive adhesive material is processed.

The method for producing the pressure-sensitive adhesive material of the present invention employs a process of treating the surface of the adhesive layer with water, thereby preventing the adhesive layer from adhering to the roll when uncured. This makes it possible to use extremely shortened curing equipment using rolls, compared to manufacturing methods that use long linear heat curing equipment.

The adhesive composition used in the method for producing a pressure-sensitive adhesive material of the present invention comprises (1) an active hydrogen group-containing compound, (B) a tackifier, and (0) a polyisocyanate compound. Here, (4) active hydrogen group-containing compounds include ethylene glycol, psibylene glycol, 1
．． Low molecular weight alcohols such as 4-butanediol, glycerin,) limethylolpropane, 1,2.6-hexanesyliol, and pentaerythritol; ethylenediamine, 4,4'-methylene-bis-2-chloroaniline,
．． Polyether polyols, such as propylene oxide adducts of bisphenol, obtained by addition polymerizing alkylene oxides such as ethylene oxide and propylene oxide to amine compounds such as 4-methylene-bis-2-ethylaniline, or low-molecular polyols or amine compounds. and so on. Furthermore, ethylene dalycol,
Polyhydric alcohols such as propylene glycol and 1,4-butanediol: t-k and 7-tal ale malein st v
Examples include polyester glycols, acrylic polyols, castor oils, tall oils, etc., which are condensation polymers with polysalts such as phosphoric acid, succinic acid, adipic acid, and terephthalate, and have a hydroxyl group at the end. There are also liquid rubbers having active hydrogen groups such as hydroxyl groups, amino groups, imino groups, carmexyl groups, and mercapto groups at the molecular ends.

These liquid rubbers have a number average molecular weight of 500 to 25
000 diene polymers with 4 to 12 carbon atoms, copolymers, and even these diene monomers! - and an α-olefinic addition polymerizable monomer having 2 to 22 carbon atoms. Specifically, polybutadiene homopolymer, l-isoprene homopolymer, butadiene-isoprene copolymer, butadiene-styrene polymer, butadiene-acrylonitrile polymer! -, butadiene-2-ethylhexyl acrylate copolymer, butadiene-l-otatadecyl acrylate copolymer! - etc. Among these, those having a viscosity of 2000 mm or less at room temperature are preferred, and those with a viscosity of 500 mm or less are more preferred. In addition, as for its fine structure, liquid goo having 1.4 bonds of 50 or more is preferably used.

As mentioned above, there are many types of active hydrogen group-containing compounds, and there are no particular restrictions on their types, but they may be compatible with the tackifying substances described below or have a wide range of compoundability. From the viewpoint of water resistance and the like, it is preferable to use a liquid rubber having active hydrogen groups alone or in combination with other compounds.

Next, as the (B) tackifying substance used in the present invention,
There are bituminous substances and tackifying resins. There is no particular restriction on the bituminous material, and straight asphalt, semi-brown asphalt, blown asphalt, or a mixture thereof can be exemplified. Next, as the tackifier resin, alkylphenol resin, terpene 41tlli,
Terpene phenol tung fat, xylene formaldehyde resin, agin.

Examples include hydrogenated rosin, rimalone resin, aliphatic and aromatic petroleum resins, and the like. As these tackifying substances, those having a softening point of about 40 to 150°C are used.

The amount of this tackifying substance is 10 to 1000 parts by weight, preferably 20 to 600 parts by weight, based on 100 parts by weight of the atomic group-containing compound, depending on the purpose of use of the pressure-sensitive adhesive material to be produced and the thickness of the adhesive layer. This is within the scope of the department. The amount of compounding also varies depending on the type of active hydrogen group-containing compound, and as mentioned above, by using a liquid rubber containing active hydrogen groups, it is possible to increase the amount of compounding, and as a result, the cost of the adhesive is significantly reduced. becomes cheaper. Therefore, by increasing the thickness of the adhesive layer, it can be used not only as a pressure-sensitive adhesive but also as a damping material with adhesive properties, for example.

Next, the (0)l reinocyanate compound used in the present invention is an organic compound having two or more isocyanate groups in one molecule, and is reactive with the active hydrogen group of the active hydrogen group-containing compound. It has an isocyanate group. Such l-inocyanate compounds are well known, and are prepolysiloxane compounds having terminal isocyanate groups obtained by reacting lyol isocyanate in advance. It may also be a compound with a - symbol. Examples of isocyanate compounds include the usual aromatic, aliphatic and aliphatic compounds, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, liquid habitual diphenylmethane diisocyanate, l. Methylene phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenyl diisocyanate, naphthalene-1,5-
Examples include diisocyanate F, isopropylbenzene-2°4-diisocyanate, and addition reaction products of polypropylene glyfur and silylene diisocyanate.

These polyisocyanate compounds act as a curing or crosslinking component of the active hydrogen group-containing compound, and the amount of the inocyanate compound is usually determined from CLS to (198 , more preferably determined to be α4~(L?5 equivalent). If this amount is too small, less than 113, the adhesive strength is too small to withstand practical use, and the heat resistance and cold resistance are also poor. Moreover, if the amount exceeds α98 and is blended in excess, the heat resistance and cold resistance are good, but the adhesion strength decreases significantly, which is not preferable.

As detailed above, the adhesive composition used in the present invention is
(4)l (B) # Although the five components of (0) are essential, there is no restriction on adding other auxiliary agents as necessary. The method of addition is not particularly limited either, but it is advantageous to add it before adding the polyisocyanate compound and thoroughly mix it.

The auxiliary agents used include (1) urethane catalysts such as di-n-butyltin dilaurate, stannous octoate, triethylene cyanoate, diethylene cyanochloride, ethylamine, metal salts of otatilic acid, and the like; ,(
2) Geotatilphthalate.

Viscosity modifier such as process oil, (3) Cardan platter. Calcium carbonate, clay, talc,! Fillers for squid, various fiber materials, etc. (4) Anti-aging agents.

Antioxidant, ultraviolet 1IiI @ collector halide stabilizer, ml
There are 1g agents, colorants, etc.

Next, a method for manufacturing the pressure-sensitive adhesive material of the present invention will be explained.

First, (4) the active hydrogen group-containing compound, the tackifying substance, and any necessary auxiliary agents are added and mixed uniformly using a Banbury mixer, kneader, etc., and then the polyisocyanate compound is added and mixed thoroughly. do. When there is a large amount of mixture to be mixed, it is preferable to use a multi-component continuous mixer.

Next, this mixture is coated and cast onto a support as it is or via an undercoat layer using a reverse coater, kiss coater, knife coater, extruder, etc. to form an adhesive layer. The support may be arbitrarily selected from woven paper, metals such as aluminum, films or sheets of cellophane, gillyester, laryamide, polyvinyl chloride, polyethylene, polypropylene, etc. depending on the purpose of use. Moreover, the thickness of the adhesive layer formed on the support is usually 20μ or more, and the adhesive tape,! ! It can be manufactured in a wide range of applications, from applications such as foiling to applications with other functions such as anti-corrosion sheets and distribution sheets, ie, in the range of several square meters.

The support, on which the adhesive layer has been formed, is introduced into a heating furnace where the adhesive layer is cured under conditions of 40 to 100°C to prevent flow, stringiness, and adhesive transfer to the release paper. However, a feature of the present invention is that the surface of the adhesive layer is treated with water before the curing reaction of the adhesive layer is completed. Treatment methods using water include immersion in water or hot water, spraying with water or steam, and a combination of these methods.

By treating this water, the adhesive layer before the curing reaction is completed is...
This makes it possible to use compact equipment with a shortened curve that uses rolls that could not previously be used in this curing process due to their tackiness.

The present inventors thought that it would be possible to some extent to lower the adhesive force between the adhesive layer and the adhesive layer by allowing water to exist between the adhesive layer and the adhesive layer before the curing reaction is completed, but at the same time, the adhesive layer It was assumed that the curing reaction on the surface of the layer was completed and the adhesive strength was drastically reduced, making it impossible to obtain a material with performance as a pressure-sensitive adhesive material. However, according to the inventors' experiments,
Surprisingly, there are no problems with sticking to the roll.

It was also found that the adhesion force had a completely unexpected effect of increasing the size of large and medium sized particles (large and medium) compared to when no water was used. These facts were only revealed through research by the present inventors. belongs to.

After the pressure-sensitive adhesive material thus obtained has undergone a curing reaction for viewing and listening, a release paper is layered on top of the material and the material is wound into a roll to form a product.

As described in detail above, the method of the present invention makes it possible to carry out the curing reaction step of the adhesive layer using significantly reduced equipment compared to conventional manufacturing methods. Therefore, productivity is improved and manufacturing costs are significantly reduced. Furthermore, the thickness of the adhesive layer can be changed freely, providing a wide variety of products. Furthermore, it has also made it possible to provide an adhesive material with greatly improved adhesive performance.

The pressure-sensitive adhesive material obtained by the method of the present invention leaves unreacted active hydrogen groups and, in combination with a tackifier, has excellent self-adhesive properties. In addition, the selection of the type of active hydrogen group-containing compound and tackifying substance, the amount of compounding,
Furthermore, by adjusting the ratio of isocyanate groups to active hydrogen groups, it is possible to manufacture materials with adhesive strength levels appropriate for the purpose of use.

Therefore, the pressure-sensitive adhesive material obtained by the production method of the present invention can be used as an adhesive tape, an insulating tape, or an anticorrosion tape.

Example Liquid polybutadiene with terminal hydroxyl group (number average molecule 1
i280G, viscosity 50M4z (io'e), hydroxyl group content αa s mq/f e fine structure trans-1°4
60%, cis-1,420%, vinyl-1゜220%)
1oo parts by weight, straight asphalt (do/80)
150 parts by weight, J-ho-butyltin dilaure) (10
After thoroughly mixing 5 parts by weight at 70°C, polymethylene polyphenylisocyanate (incyanate content 5 (
16 weight fIk%) 7 parts by weight (110010H-α65)
was added and stirred to obtain an adhesive composition. This adhesive composition was applied onto a cotton cloth and applied for 2 minutes and 1 hour after adding the polyisocyanate.
After 5 minutes and 90 minutes, soak in water and take out after 60 minutes.
A pressure-sensitive adhesive material was obtained by drying at 0° C. for 1 hour. The curing time of this adhesive composition is about 15 minutes at 65°C.

In this case, no adhesion to the metal roll was observed after immersion in water.

The resulting pressure-sensitive adhesive material was placed on the adherend with its adhesive side facing down, and a 5-reel was run three times to apply a load, and the beer strength was measured at 180 degrees after 24 hours.

The results are shown in the table.

[Brief explanation of the drawing]

FIG. 1 is a detailed explanatory diagram of the present invention. DESCRIPTION OF SYMBOLS 1...Adhesive composition, 2...Support, S...Release paper, 4...Pressure sensitive adhesive material 1.5...Doctor knife, M...Curing reaction zone, B... ...Water treatment patent applicant Idemitsu Kosan Co., Ltd. Figure 1 Touoooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo @ procedural amendment (spontaneous) November 27, 1980 Commissioner of the Japan Patent Office Shima 1) Haru Yanagi゛ Case 0 Indication / Patent Application 1982-105488 2 Name of the invention Method for producing pressure-sensitive adhesive material S Person who makes the amendment Relationship to the case Patent applicant Idemitsu Kosan Co., Ltd. 4 Agent Address: 04 Chuo, Tokyo No. 1-10, 1-chome, Kyobashi-ku Support (
that's all)

Claims (1)

[Scope of Claims] 1) A method for forming an adhesive layer on a support, comprising an adhesive composition comprising (A) an active hydrogen group-containing compound, (B) a tackifying substance, and (0) a polyisocyanate compound. A method for producing a pressure-sensitive adhesive material, which comprises treating the surface of an adhesive layer with water before completing a curing reaction. 2) The manufacturing method according to claim 1, wherein the tackifying substance is Gansei cut substance and/or tackifying resin. S) The ratio of active hydrogen groups to incyanate groups is 1t (L
S-(196 (equivalent ratio)) The manufacturing method according to item 1 or 2.