JP6931964B2 - Adhesive products and manufacturing methods for adhesive products - Google Patents

Description

The present invention relates to an adhesive product that can be applied as a glue product for fastening paper.

Conventionally, adhesive products have been widely used not only for office use but also for general households for the purpose of sealing papers such as sealing envelopes. The adhesive product includes liquid glue called water glue or adhesive, solid glue that is molded by itself and wears off its shape during use, and liquid glue is atomized from the container. Various glue products up to such as spray glue sprayed on (see, for example, Patent Document 1) are included. In addition, as such an adhesive product, a so-called pressure-sensitive transfer type adhesive tape, which is previously applied to a tape, is wound and held in a container, and is transferred to the paper by being pressed together with the tape against the paper. Those are also widely used (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 05-043854 Japanese Patent No. 5234556

However, in the above-mentioned glue products such as those described in Patent Document 1, when a sufficient amount of glue is attached to the paper, the paper is wrinkled due to the liquid component being absorbed by the paper. It can happen that it ends up. Such wrinkles are known as a characteristic that does not meet the demands of some users because the shape of the traces of using the glue product changes from before use.

On the other hand, in the case of the pressure-sensitive transfer type adhesive tape as described in Patent Document 2, since only the adhesive is transferred to the surface of the paper, there is no possibility that any liquid material will soak into the paper and wrinkles will occur. Is never formed. However, in the case of such a pressure-sensitive transfer type adhesive tape, if an adhesive is used, the tape that functions as a base material for holding the adhesive in the container is consumed. That is, the tape as a resource in an amount corresponding to the use of the adhesive must be discarded.

The present invention focuses on such a defect, and an object of the present invention is to provide an adhesive product capable of effectively suppressing deformation of paper at a used portion while avoiding waste of resources.

The present invention has taken the following measures in order to achieve such an object.

That adhesive products of the present invention is the content of the alcohol of 2-4 carbon atoms 99 wt% or more and a dispersion medium containing water less than 1 wt%, Rineba wear such dispersed in the dispersion medium It comprises a pressure-sensitive adhesive composition for forming an agent, contains 25 to 45 parts by weight of a dispersion medium, and 55 to 75 parts by weight of the pressure-sensitive adhesive, so that it can be applied little by little to the paper to be coated. The pressure-sensitive adhesive composition is dispersed in a dispersion medium in a polymer state to form an emulsion, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive is JIS. Under the conditions according to Z 0237-8, the composition ratio of the adhesive strength composition was adjusted to 67%, coated on a corona-treated PET film with a thickness of 50 μm, and left for 1 minute to disperse the dispersion medium. After volatilizing, it is processed into a strip of 10 mm x 150 mm, attached to a stainless steel plate treated according to JIS Z 0237-8, and attached while pressurizing 5 mm / s x 1 reciprocating with a 2 kg kg roller. It is characterized in that it is 2.0 N / cm or more when the peeling resistance is measured at a speed of 300 mm / min by Autograph (registered trademark) (manufactured by Shimadzu Corporation) after 40 minutes .

Here, the so-called lower alcohol, in which the alcohol in the dispersion medium has 2 to 4 carbon atoms, has little effect on the human body and is suitable for use in office work where the user may come into direct contact with the body. Because it is. Further, if the water content is more than 6%, it takes too much time to volatilize after application, and the possibility of wrinkles being formed on the paper increases during that time.

In such a case, the dispersion medium applied to the paper evaporates rapidly from the paper because it has a large amount of highly volatile alcohol components and a low water content with respect to the whole. As a result, only the adhesive can be attached to the surface of the paper without forming wrinkles on the paper. Of course, the adhesive product does not require resources such as tape other than the dispersion medium. That is, according to the present invention, it is possible to provide an adhesive product capable of effectively suppressing deformation of paper at a used portion while avoiding waste of resources.

It is preferable that the alcohol concentration in the dispersion medium is higher than 90% so that the dispersion medium evaporates from the paper more quickly.

Further, it is desirable that the average particle size of the pressure-sensitive adhesive composition formed in the dispersion medium is 0.1 to 10 μm in order to appropriately exert the adhesive force. If the particle size is too small or too large, it is considered that problems such as deterioration of adhesive strength and deterioration of handling performance are caused.

In order to provide a pressure-sensitive adhesive product having a higher adhesive strength, it is preferable to form a pressure-sensitive adhesive together with the pressure-sensitive adhesive composition and include a function-imparting agent for imparting a specific function to the pressure-sensitive adhesive.

In particular, in order to more preferably exert the adhesive force, the pressure-sensitive adhesive composition is a polymer and / or a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms. desirable.

The method for producing an adhesive according to the present invention, which can suppress the problem of forming wrinkles on paper while avoiding the waste of resources such as tape, has an alcohol content of 2 to 4 carbon atoms of 99% by weight or more. in it and become by dispersing viscosity Chakuzai in a dispersion medium containing less than 1 wt% of water is used is stored in a container having a head portion that can be applied in small amounts to the paper is a coating target, the A method for producing a pressure-sensitive adhesive product in which a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive is dispersed in a dispersion medium in a polymer state to form an emulsion, wherein the pressure-sensitive adhesive is contained in the dispersion medium. A preparatory step for dissolving a monomer component and a cross-linking agent which are raw materials for the pressure-sensitive adhesive composition constituting the above, a start step for subjecting the dispersion medium, the monomer component and the cross-linking agent in the preparatory step to a reaction initiation treatment, and the above-mentioned A polymerization step of advancing the polymerization and cross-linking of the monomer component in the starting step to obtain the pressure-sensitive adhesive composition which is a polymer and / or a copolymer that disperses the monomer component in the dispersion medium, and the polymerization step. After that, it has an adjustment step of adjusting the amount of the dispersion medium so that the dispersion medium is 25 to 45 parts by weight and the pressure-sensitive adhesive is 55 to 75 parts by weight, and the adhesive strength of the pressure-sensitive adhesive is increased. , JIS Z 0237-8, the composition ratio of the adhesive strength composition was adjusted to 67%, applied on a corona-treated PET film with a thickness of 50 μm, and left for 1 minute to disperse. After volatilizing the medium, it is processed into a strip of 10 mm x 150 mm, pasted on a stainless steel plate treated according to JIS Z 0237-8, and pasted while pressurizing 5 mm / s x 1 reciprocating with a 2 kg kg roller. In total, it is characterized by being 2.0 N / cm or more when the peeling resistance is measured at a speed of 300 mm / min by Autograph (registered trademark) (manufactured by Shimadzu Corporation) after 40 minutes.

Further, since it has an adjusting step of adjusting the amount of the dispersion medium so that the amount of the dispersion medium that has undergone the polymerization step is 25 to 45 parts by weight and the amount of the adhesive material is 55 to 75 parts by weight, it is applied to paper. It is possible to manufacture an adhesive product that is easier to handle and has improved ease of use . That is, if the dispersion medium is lower than 25 parts by weight, there is a high possibility that the conditions of use by the actual user, such as ease of application and ease of storage, will not be satisfied. For example, it is conceivable that the fluidity at the time of applying the adhesive product becomes low.

Here, in the case of the pressure-sensitive adhesive product according to the present invention, the monomer dissolved in the dispersion medium in the polymerization step becomes a pressure-sensitive adhesive composition which is a polymer and / or a copolymer capable of suitably constituting the pressure-sensitive adhesive. The difference between the SP values of the dispersion medium and the monomer component is less than ^{6.5 (MPa) 1/2} as an embodiment that reliably satisfies such a requirement that the dispersion medium must sometimes be precipitated without being dissolved. It can be mentioned that the difference between the SP value of the dispersion medium and the polymer is 6.5 (MPa) ^{1/2 or more.} Here, the SP value (δ: solubility parameter) of the constituent component is calculated by Fedors [“Polymer Eng. & Sci.”, Vol. 14, No. 2 (1974), No. 148. See page 154] That is,

（ただしΔｅｉは原子又は基に帰属する２５℃における蒸発エネルギー、Δｖｉは２５℃におけるモル体積である）にて計算して求めることができる。

(However, Δei is the evaporation energy at 25 ° C. attributable to the atom or group, and Δvi is the molar volume at 25 ° C.).

In order to allow the polymerization step to proceed smoothly, it is preferable to carry out the polymerization step in an inert gas atmosphere.

According to the present invention, it is possible to provide an adhesive product capable of effectively suppressing deformation of paper at a used portion while avoiding waste of resources.

The external view of the adhesive product which concerns on one Embodiment of this invention. Explanatory drawing of the same action. Explanatory drawing which concerns on the manufacturing method which concerns on the said embodiment. Same as above. Same as above. Same as above. Explanatory drawing which concerns on the manufacturing method which concerns on the modification of the said embodiment. Same as above. The operation explanatory drawing of the adhesive product which concerns on the modification. Explanatory drawing for demonstrating embodiment of this invention. The figure which shows the characteristic of the same Example as a table. The figure which shows the test result of the same Example as a table.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

The pressure-sensitive adhesive product A according to the present embodiment contains a pressure-sensitive adhesive G composed mainly of a polymer P as a polymer (and / or a copolymer) with respect to a liquid containing alcohol AL as a dispersion medium. It is dispersed. As shown in FIG. 1, for example, it is stored in an airtight container and passes through the shape of a container such as a head portion that can be applied little by little to the paper PA to the paper PA, for example, at a thickness of 50 μm. By being applied, it volatilizes from the surface of the paper PA without permeating into the inside of the paper PA within a time such as within 10 seconds. As a result, as shown in FIG. 2, for example, the pressure-sensitive adhesive G having a thickness of about 15 μm is applied to the surface of the paper PA. In addition, the adhesive strength of the pressure-sensitive adhesive G applied on the paper PA is, for example, about 0.5 N / cm, more specifically 1.5 N / cm or more, and more specifically 2.0 N / cm or more. It has a sufficiently excellent adhesive strength as a glue product that is usually used.

Here, the pressure-sensitive adhesive product A according to the present embodiment includes a dispersion medium in which alcohol AL having 2 to 4 carbon atoms is 90% by weight or more, and a pressure-sensitive adhesive composed of a pressure-sensitive adhesive composition dispersed in the dispersion medium. It is characterized by having. In the present embodiment, the dispersion medium is referred to as alcohol AL because most of the dispersion medium is alcohol AL, which is more than 94% by weight and further 99 % by weight or more.

Examples of the alcohol AL having 2 to 4 carbon atoms include ethanol, butanol, propanol and isopropanol. Here, the so-called lower alcohol AL, in which the alcohol AL in the dispersion medium has 2 to 4 carbon atoms, has little effect on the human body and is likely to come into direct contact with the body for office use. This is because it is suitable for use. If the alcohol AL concentration in the dispersion medium is lower than 90% by weight , it takes too much time for the dispersion medium other than the alcohol AL to volatilize after application, or wrinkles W are formed on the paper PA during that time. This is because the possibility of getting rid of it increases.

The pressure-sensitive adhesive composition is preferably an alkyl group having 1 to 20 carbon atoms, particularly a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 16 carbon atoms from the viewpoint of easily balancing the adhesive properties. Polymers (and / or copolymers) can be mentioned. Examples of the (meth) acrylic acid alkyl ester constituting the polymer (and / or copolymer) of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and (meth). Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, Isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate , (Meta) isononyl acrylate, (meth) decyl acrylate, (meth) isodecyl acrylate, (meth) undecyl acrylate, (meth) dodecyl acrylate, (meth) tridecyl acrylate, (meth) tetradecyl acrylate, Alkyl with 1 to 20 carbon atoms such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, and eicocil (meth) acrylate. A (meth) acrylic acid alkyl ester having a group can be mentioned. As a preferred example thereof, lauryl methacrylate (dodecyl (meth) acrylate) is used in the present embodiment.

Further, the main component of the pressure-sensitive adhesive composition is not limited to the above, and can be appropriately selected as long as it does not deviate from the gist of the present invention. For example, a fatty acid vinyl copolymer is mentioned, and an ethylene-vinyl acetate copolymer is preferably used both characteristically and economically. Examples of fatty acid vinyl ester compounds include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, and versatic acid. Examples include vinyl. In addition to ethylene and vinyl acetate, an ethylenically unsaturated monomer copolymerizable within a range that does not impair the properties may be copolymerized, and examples of such a monomer include propylene, 1-butene, and the like. Olefins such as isobutene, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 3,4-dihydroxy-1-butene, 5-hexene-1,2-diol, etc. Hydroxy group-containing α-olefins and derivatives such as esterified products thereof, for example, 3,4-diacetoxy-1-butene, acryloacid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, Unsaturated acids such as (anhydrous) itaconic acid or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamide propane. Sulfonic acid or a salt thereof, acrylamides such as acrylamide propyldimethylamine or an ester thereof or a quaternary salt thereof, methacrylamide, N-alkylmethacrylicamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylate, 2-methacryl Methalamides such as amide propanesulfonic acid or a salt thereof, methacrylicamide propyldimethylamine or an ester thereof or a quaternary salt thereof, N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acrylic Vinyl cyanide such as nitrile and methacrylnitrile, vinyl ethers such as alkyl vinyl ether having 1 to 18 carbon atoms, hydroxyalkyl vinyl ether and alkoxyalkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide and the like. Vinyl halides, vinylsilanes such as trimethoxyvinylsilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamide-3-dimethylpropyl) -ammonyl chloride, acrylamide-2-methylpropanesulfon Acids, vinylethylene carbonate, glycerin monoallyl ether and the like can be mentioned.

Further, it is desirable that the average particle size of the polymer P formed in the dispersion medium is 0.1 to 10 μm in order to appropriately exert the adhesive force. If the particle size is too small or too large, it is considered that problems such as deterioration of adhesive strength and deterioration of handling performance are caused. In the present embodiment, the particle size of the polymer P is 0.5 to 5 μm, specifically 3.96 μm.

In addition to the polymer P, the pressure-sensitive adhesive G contains a function-imparting agent Q (FIG. 6) including a pressure-imparting resin usually called Takifire. As the tackifier resin, known ones can be appropriately used without particular limitation. Specific examples of the tackifier resin include rosin-based resin, terpene-based resin, aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, alicyclic petroleum resin, xylene resin, and elastomer. Can be mentioned. Further, as another preferable example of the function-imparting agent Q, for example, various colorants can be mentioned. Further preferable examples include, for example, a pH indicator and a photochromic compound that develop a color when the pressure-sensitive adhesive product A is applied and become colorless in the air after the coating so that the coating marks of the pressure-sensitive adhesive product A can be made inconspicuous.

The adhesive G of this embodiment is made mainly of a polymer P is the polymer (and / or copolymer), dispersion medium is evaporated from when applied to paper PA in the coating Nuno圧50μm stop The time required to reach the ready-to-wear state is 10 seconds or less, preferably 5 seconds or less, and the adhesive strength after the required time is 0.5 N / cm or more. In addition, in this embodiment, the molecular weight of the polymer P is set to 400,000 or more in order to preferably exert the adhesive force. As a result, the particle size is easy to handle and the adhesive strength is high.

Here, the "fixable state" in the present embodiment means that the dispersion medium is sufficiently volatilized from the paper PA, and the pressure-sensitive adhesive G remains in a layer on the surface of the paper PA, and is constant to the pressure-sensitive adhesive G. It refers to a state in which the pressure-sensitive adhesive G can be fastened to an object to be fastened by the above pressing by an external force, in other words, a state in which the pressure-sensitive adhesive G can function as a pressure-sensitive pressure-sensitive adhesive.

Then, the production of the pressure-sensitive adhesive G according to the present embodiment, which can suppress the problem of forming wrinkles W on the paper PA while avoiding the waste of resources such as the pressure-sensitive adhesive holding tape used for the pressure-sensitive transfer type pressure-sensitive adhesive tape. The method is a method for producing a pressure-sensitive adhesive product A in which a pressure-sensitive adhesive G containing a pressure-sensitive adhesive composition which is a polymer P is dispersed in a dispersion medium containing 99 % by weight or more of alcohol AL having 2 to 4 carbon atoms.

That is, as shown in FIG. 3, in other words, the preparation step S1 in which the monomer component M and the cross-linking material B are dissolved in the alcohol AL as the dispersion medium, and the monomer dissolved in the alcohol AL as the dispersion medium in the preparation step S1. The reaction initiation step S2 as shown in FIG. 4 in which the reaction initiation treatment is applied to the component monomer M and the cross-linking material B, and the polymerization of the monomer component and the crosslinking material B in the reaction initiation step S2 are allowed to proceed, and the alcohol AL as a dispersion medium is allowed to proceed. It is characterized by having a polymerization step S3 as shown in FIG. 5, which is carried out in an oxygen-free atmosphere as a pressure-sensitive adhesive composition which is a polymer P dispersed therein.

In the preparation step S1, in addition to the above-mentioned monomer M and cross-linking material B, the dispersion stabilizer ST is also added in the present embodiment. The cross-linking agent B can be variously set according to the above-mentioned monomer M. Here, divinylbenzene can be mentioned as a material that can be used as the cross-linking material B. As a preferred example thereof, in the present embodiment, the divinylbenzene is added so as to be contained in an amount of 0.05% by weight based on the adhesive product A which is a finished product. Further, as an example of the preferable dispersion stabilizer ST, polyvinylpyrrolidone is used in this embodiment.

In the present embodiment, the reaction initiation step S2 is a step of adding benzoyl peroxide as the reaction initiator Z. The reaction start step S2 is, of course, appropriately selected according to the type and amount of the cross-linking agent B. Needless to say, as an example in which the reaction start step S2 can be realized, not only the addition of a substance but also a process such as heating or UV irradiation is included in the process of initiating the polymerization reaction.

In the present embodiment, the polymerization step S3 is performed in an inert gas IG atmosphere such as nitrogen or a rare gas as described above. This is for the purpose of preventing the polymerization reaction by the cross-linking agent B from being hindered by oxygen in the air. Moreover, of course, it does not deny other methods for effectively removing oxygen in the air.

In particular, in the present embodiment, the adjustment step S4 shown in FIG. 6 for adjusting the amount of the dispersion medium so that the dispersion medium that has undergone the polymerization step S3 is 25 to 45 parts by weight and the pressure-sensitive adhesive G is 55 to 75 parts by weight is performed. It is provided. This is because if the amount of the dispersion medium is more than 45 parts by weight, it takes too much time to volatilize, and the possibility that wrinkles W are formed on the paper PA during that time increases. On the other hand, if the alcohol AL as the dispersion medium is lower than 25 parts by weight, there is a high possibility that the conditions of use by the actual user, such as ease of application and ease of storage, are not satisfied. Further, in the present embodiment, the adjustment step S4 includes a procedure of adding the function-imparting agent Q containing the tackifier in addition to the adjustment of the alcohol AL concentration, but of course, the timing of adding the function-imparting agent Q is The adjustment step is not limited to S4, and may be performed at the same timing as, for example, the preparation step S1.

In addition, in the present embodiment, when the monomer M, which is a monomer dissolved in the dispersion medium in the polymerization step S3, becomes the polymer P, which is a polymer capable of suitably forming the pressure-sensitive adhesive G, a dispersion medium such as alcohol AL is used. Must precipitate without being dissolved from the polymer. In this embodiment, the difference between the SP values of the dispersion medium and the monomer component is less than ^{6.5 (MPa) 1/2} , and the difference between the SP values of the dispersion medium and the polymer is as an embodiment that reliably satisfies such a requirement. The dispersion medium and the monomer component in the preparation step S1 are specified so that is 6.5 (MPa) ^{1/2 or more.}

<Modification example>
Hereinafter, modifications of the present embodiment will be described with reference to FIGS. 6 to 9. Regarding the modified example, the same reference numerals are given to the configurations or steps according to the above-described embodiment, and the same reference numerals are given to those corresponding to the present modified example, and detailed description thereof will be omitted.

In the above embodiment, in the polymerization step S3, an embodiment of producing a polymer P which is a polymer (and / or a copolymer) from a single type of monomer M has been disclosed, but of course, a method for producing an adhesive product A according to the present invention. May prepare a pressure-sensitive adhesive composition from a plurality of types of monomers. That is, this modification is performed as follows after the preparation step ST1, the reaction start step S2, and the polymerization step S3 are carried out in the same manner as in the above embodiment.

That is, in this modification, as shown in FIG. 7, after the polymerization step S3, a monomer M'of a different type from the monomer M and the reaction initiator Z are further added, and then the polymerization is carried out in the alcohol AL as the dispersion medium. The polymerization step S31 is performed. This creates a copolymer CP. In this case, after the second polymerization step S31, the second adjustment step S41 similar to the adjustment step in the above embodiment is performed.

As shown in FIGS. 8 and 9, the pressure-sensitive adhesive produced in this manner is in a state in which the pressure-sensitive adhesive G, which is the main component of the pressure-sensitive adhesive composition, is dispersed in the alcohol AL which is the dispersion medium. In addition to the copolymer, the pressure-sensitive adhesive composition also contains a small amount of polymer P'in which only the monomer M'added in the second polymerization step S31 was polymerized, and polymer P in which the reaction did not proceed from the polymerization step S3. there is a possibility.

Here, in the copolymer CP, the monomer M'is crosslinked and polymerized around the polymer P with the polymer P crosslinked and polymerized in the polymerization step S3 as a so-called "nucleus". As a result, the copolymer CP has a double structure, specifically a core-shell structure, as schematically shown in FIG.

As shown in FIG. 9, in the adhesive product A thus produced, the alcohol AL volatilized immediately after application as in the above embodiment, and the copolymer CP became the main component of the adhesive composition on the surface of the paper PA. Only the pressure-sensitive adhesive G is applied in layers. Moreover, as in the above embodiment, no wrinkles W are formed on the paper PA, and the paper PA can be preferably fixed to an object to be fastened such as other paper.

Although the embodiments and modifications of the present invention have been described above, the specific configuration of each part is not limited to the above-described embodiments and modifications, and various modifications are made without departing from the spirit of the present invention. Is possible.

For example, in the above embodiment, the embodiment in which the present invention is applied to an adhesive product used as a so-called water paste is disclosed, but of course, it is applied to an embodiment in which a required amount of the adhesive product is discharged from an adhesive of a type applied by a brush or a nozzle. It may be the one that has been used. Further, the specific embodiment of the monomer and the cross-linking agent is not limited to those of the above-described embodiment and modified examples, and various embodiments including existing ones can be applied.

In addition, the specific configuration of each part is not limited to the above-described embodiment and modification, and various modifications can be made without departing from the spirit of the present invention.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

In the examples that satisfy the conditions of the adhesive product shown in the above embodiment, as shown on the left side of FIG. 10, the adhesive adheres to the paper in a state where wrinkles are not formed when the surface of the paper is applied, but the same applies. In addition, in the case of a comparative example that can be used as a so-called water glue, wrinkles are formed on the paper at least in part as shown on the right side of the figure. In this specification, for convenience, an example in which the emulsion itself cannot be produced as shown on the right side of FIG. 10 is also described as a comparative example.

Hereinafter, examples, comparative examples, and reference examples of the present invention will be described.

<Test material>
This time, as shown as a table in FIG. 11, Examples 1 to 4 included in claim 1 of the present application, and Comparative Examples 1 and 2 not included in the same claim 1 are prepared. Further, as described above, in Comparative Example 2 below, an emulsion itself in which the pressure-sensitive adhesive composition was dispersed in a dispersion medium, which is an intermediate compound, could not be obtained, but is described as a comparative example as it is in the present specification.

<Example 1>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 250 g of lauryl methacrylate as a monomer component, 0.100 g of divinylbenzene as a cross-linking agent, 625 g of Solmix AP-7 (manufactured by Japan Alcohol Trading Co., Ltd.) as a dispersion medium, that is, an alcohol mainly composed of ethanol, and polyvinylpyrrolidone as a dispersion stabilizer. After the preparatory step in which 6.25 g of (ave. Mol wt 400000) was added, 0.80 g of benzoyl peroxide (containing 25 wt% water), which is a reaction initiator, was added and stirred at 250 rpm to serve as the reaction initiation step. While dissolving the reagent. After the reagent was dissolved, argon was bubbled at a flow rate of 200 ml / min for 30 minutes to maintain an environment in which oxygen was removed. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization, that is, a polymerization step was performed for 48 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After completion of the polymerization, a white emulsion was obtained and no agglutination was observed. The average particle size (D50) of the obtained emulsion was 3.6 μm, the solid content concentration was 32% by weight, and the polymerization rate (measurement by nuclear magnetic resonance method: hereinafter referred to as ¹ H-NMR) was 100%.

Then, with respect to the emulsion for producing the adhesive product obtained by the above method, the composition ratio of the polymer, which is the adhesive composition which is an adhesive microsphere, is adjusted to 67% by centrifugation or the like, and the adhesive product is obtained. Example 1 was used to evaluate the suitability of the product. That is, in the first embodiment, a dispersion medium in which alcohol having 2 to 4 carbon atoms is 99 % by weight or more and the water content is less than 1 % by weight is dispersed in the dispersion medium to form a pressure-sensitive adhesive. Corresponds to a pressure-sensitive adhesive product, which comprises a pressure-sensitive adhesive composition for the purpose. Specifically, in Example 1, the alcohol content of the dispersion medium is 99.97 % by weight , and the water content is 0.03% by weight.

Here, in the adhesive product according to Example 1, the difference in SP value between the dispersion medium and the monomer component is ^{less than 6.5 (MPa) 1/2} , and the difference in SP value between the dispersion medium and the polymer is It satisfies the requirement of 6.5 (MPa) ^{1/2 or more.}

<Example 2>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 250 g of lauryl methacrylate, 0.075 g of divinylbenzene, which is a smaller amount than that of Example 1, 625 g of Solmix AP-7 (sold by Nippon Alcohol), 6.25 g of polyvinylpyrrolidone (ave. Mol wt 400000), and peroxidation. 0.80 g of benzoyl (containing 25 wt% water) was added, and the reagent was dissolved with stirring at 250 rpm. After dissolving the reagent, argon was bubbled at a flow rate of 200 ml / min for 30 minutes. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization was carried out for 24 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After completion of the polymerization, a white emulsion was obtained and no agglutination was observed. The average particle size (D50) of the obtained emulsion was 4.0 μm, the solid content concentration was 31% by weight, the water content was 0%, and the polymerization rate ( ¹ H-NMR) was 100%.

Then, with respect to the emulsion for producing the adhesive product obtained by the above method, the composition ratio of the polymer, which is the adhesive composition which is an adhesive microsphere, is adjusted to 67% by centrifugation or the like, and the adhesive product is obtained. In Example 2, the suitability of the product was evaluated. That is, in the second embodiment, a dispersion medium in which alcohol having 2 to 4 carbon atoms is 99 % by weight or more and the water content is less than 1 % by weight is dispersed in the dispersion medium to form a pressure-sensitive adhesive. Corresponds to a pressure-sensitive adhesive product, which comprises a pressure-sensitive adhesive composition for the purpose. Specifically, in Example 2, the alcohol content of the dispersion medium is 99.97 % by weight , and the water content is 0.03% by weight.

Here, in the adhesive product according to Example 2, the difference in SP value between the dispersion medium and the monomer component is ^{less than 6.5 (MPa) 1/2} , and the difference in SP value between the dispersion medium and the polymer is It satisfies the requirement of 6.5 (MPa) ^{1/2 or more.}

<Example 3>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 125 g of palmityl / stearyl methacrylate, 0.040 g of divinylbenzene, 312.5 g of Solmix AP-7 (manufactured by Nippon Alcohol Sales), 3.125 g of polyvinylpyrrolidone (ave. Mol wt 400000), and benzoyl peroxide (25 wt% water content). ) 0.40 g was added, and the reagent was dissolved while stirring at 250 rpm. After dissolving the reagent, argon was bubbled at a flow rate of 200 ml / min for 30 minutes. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization was carried out for 24 hours. Then, a mixed solution of 62.5 g of lauryl methacrylate, 156.3 g of Solmix AP-7 (manufactured by Japan Alcohol Trading Co., Ltd.), and 0.20 g of benzoyl peroxide (containing 25 wt% water) was added dropwise to the reaction vessel over 3 hours. Then, the second polymerization step was carried out by carrying out polymerization for 24 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After completion of the polymerization, a white emulsion was obtained and no agglutination was observed. The average particle size (D50) of the obtained emulsion was 2.9 μm, the solid content concentration was 30% by weight, and the polymerization rate ( ¹ H-NMR) was 100%.

Then, with respect to the emulsion for producing the adhesive product obtained by the above method, a second adjustment step is performed to adjust the composition ratio of the copolymer, which is an adhesive composition which is an adhesive microsphere, to 67% by centrifugation or the like. Was used as Example 3 for evaluating the suitability as an adhesive product. That is, in Example 3, a dispersion medium in which alcohol having 2 to 4 carbon atoms is 99 % by weight or more and the water content is less than 1 % by weight is dispersed in the dispersion medium to form a pressure-sensitive adhesive. Corresponds to a pressure-sensitive adhesive product, which comprises a pressure-sensitive adhesive composition for the purpose. In addition, the pressure-sensitive adhesive microspheres contained in Example 3 have a so-called core-shell structure as schematically shown in FIG. Specifically, in Example 3, the alcohol content of the dispersion medium is 99.97 % by weight , and the water content is 0.03% by weight.

Here, the adhesive product according to Example 3 has a difference in SP value between the dispersion medium and the monomer component of ^{less than 6.5 (MPa) 1/2} , and the dispersion medium and the copolymer having the core-shell structure. It satisfies the requirement that the difference between the SP values of is 6.5 (MPa) ^{1/2 or more.}
<Example 4>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 250 g of lauryl methacrylate as a monomer component, 0.100 g of dimethacrylate 1,6-hexanediol as a cross-linking agent, and 625 g of Solmix AP-7 (manufactured by Japan Alcohol Trading Co., Ltd.), which is an alcohol mainly composed of a dispersion medium, that is, ethanol. After the preparatory step in which 6.25 g of polyvinylpyrrolidone (ave. Mol wt 400000), which is a dispersion stabilizer, was added, 0.80 g of benzoyl peroxide (containing 25 wt% water), which is a reaction initiator, was used as the reaction initiator step. Was charged, and the reagent was dissolved while stirring at 250 rpm. After the reagent was dissolved, argon was bubbled at a flow rate of 200 ml / min for 30 minutes to maintain an environment in which oxygen was removed. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization, that is, a polymerization step was performed for 48 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After completion of the polymerization, a white emulsion was obtained and no agglutination was observed. The average particle size (D50) of the obtained emulsion was 4.0 μm, the solid content concentration was 31% by weight, and the polymerization rate ( ^{denoted as 1 1} H-NMR) was 100%.

Then, with respect to the emulsion for producing the adhesive product obtained by the above method, the composition ratio of the polymer, which is the adhesive composition which is an adhesive microsphere, is adjusted to 67% by centrifugation or the like, and the adhesive product is obtained. In Example 4, the suitability of the product was evaluated. That is, in the fourth embodiment, a dispersion medium in which alcohol having 2 to 4 carbon atoms is 99 % by weight or more and the water content is less than 1 % by weight is dispersed in the dispersion medium to form a pressure-sensitive adhesive. Corresponds to a pressure-sensitive adhesive product, which comprises a pressure-sensitive adhesive composition for the purpose. Specifically, in Example 4, the alcohol content of the dispersion medium is 99.97 % by weight , and the water content is 0.03% by weight.

Here, in the adhesive product according to Example 4, the difference in SP value between the dispersion medium and the monomer component is ^{less than 6.5 (MPa) 1/2} , and the difference in SP value between the dispersion medium and the polymer is It satisfies the requirement of 6.5 (MPa) ^{1/2 or more.}

<Comparative example 1>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 250 g of lauryl methacrylate, 556 g of Solmix AP-7 (manufactured by Nippon Alcohol Sales), 69 g of ion-exchanged water, 6.25 g of polyvinylpyrrolidone (ave. Mol wt 400000), and 0.80 g of benzoyl peroxide (containing 25 wt% water) are added. The reagent was added and the reagent was dissolved while stirring at 250 rpm. After dissolving the reagent, argon was bubbled at a flow rate of 200 ml / min for 30 minutes. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization was carried out for 24 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After completion of the polymerization, a white emulsion was obtained and no agglutination was observed. The average particle size (D50) of the obtained emulsion was 2.9 μm, the solid content concentration was 31% by weight, and the polymerization rate ( ^{calculated from 1 1} H-NMR) was 99%.

Then, with respect to the emulsion for producing the adhesive product obtained by the above method, the composition ratio of the polymer, which is the adhesive composition which is an adhesive microsphere, is adjusted to 67% by centrifugation or the like, and the adhesive product is obtained. It was set as Comparative Example 1 to evaluate the appropriateness as.

That is, in Comparative Example 1, a dispersion medium in which alcohol having 2 to 4 carbon atoms is 99 % by weight or less and the water content is higher than 1 % by weight and a dispersion medium are dispersed in the dispersion medium to form a pressure-sensitive adhesive. Corresponds to a pressure-sensitive adhesive product comprising the pressure-sensitive adhesive composition for the purpose. That is, in Comparative Example 1, specifically, the alcohol content of the dispersion medium is 87.55 % by weight , and the water content is 12.45% by weight.

However, in the adhesive product according to Comparative Example 1, the difference in SP value between the dispersion medium and the monomer component is ^{less than 6.5 (MPa) 1/2} , and the difference in SP value between the dispersion medium and the polymer is 6 The requirement of .5 (MPa) ^1/2 or more is satisfied.

<Comparative example 2>
A thermometer, a stirring blade, a bubbling tube, and a reflux tube were attached to a 2 L four-necked flask. Here, 125 g of vinyl acetate, which is a monomer component, 556 g of Solmix AP-7 (manufactured by Japan Alcohol Trading Co., Ltd.), 69 g of ion-exchanged water, 6.25 g of polyvinylpyrrolidone (ave. Mol wt 400000), and benzoyl peroxide (containing 25 wt% water). 0.80 g was added and the reagent was dissolved with stirring at 250 rpm. After dissolving the reagent, argon was bubbled at a flow rate of 200 ml / min for 30 minutes. Then, the reaction vessel was immersed in an oil bath set at 67 ° C., and polymerization was carried out for 12 hours. During the reaction, bubbling was always performed at a flow rate of 200 ml / min, and the stirring speed was 250 rpm. After the completion of the polymerization, the particles of the pressure-sensitive adhesive composition did not precipitate, and the polymer was dissolved in the liquid to be used as the dispersion medium, and the phase was separated into two phases, a solmix / ion-exchanged water mixed liquid phase, and an emulsion. Was not obtained. Therefore, it was not possible to prepare the adhesive products as in each of the above Examples and Comparative Example 1.

Here, the difference in SP value between the liquid set as the dispersion medium and the polymer is 4.4 (MPa) ^1/2 , and the difference in SP value between the liquid and the polymer is in the range of 6.5 or more. It didn't come in. For this reason, it is probable that an emulsion capable of forming an adhesive product could not be obtained. The difference in SP value between the liquid and the monomer was 5.6 (MPa) ^1/2 .

<Test method>
With respect to the emulsions obtained for producing the adhesive products according to the respective Examples and Comparative Examples 1 obtained by the above method, the polymer which is an adhesive composition which has become an adhesive microsphere by centrifugation or the like and / Alternatively, the copolymer whose composition ratio was adjusted to 67% was evaluated for its suitability as an adhesive product by measuring the adhesive strength, dryness, and the presence or absence of wrinkles on the paper according to the following test procedure.

The test for adhesive strength was carried out by a method according to JIS Z 0237-8.
First, an adhesive product in which the composition ratio of adhesive microspheres is adjusted to 67% is spread on a corona-treated PET film using a bar coater that can be applied to a thickness of 50 micron, and left for 1 minute. After volatilizing the dispersion medium, the PET film coated with the adhesive product was processed into a strip of 10 mm × 150 mm, and the coating thickness of the adhesive was measured in that state. The adhesive surface of the measurement sample was attached to a stainless steel (SUS) plate treated according to JIS Z 0237-8, and attached with a 2 kg kg roller while pressurizing 5 mm / s × 1 reciprocatingly. After 40 minutes, the peeling resistance was measured at a speed of 300 mm / min of Autograph (registered trademark) (manufactured by Shimadzu Corporation).

The dryness and the presence or absence of wrinkles on the paper were qualitatively evaluated based on the following method.
First, regarding dryness, a bar coater capable of applying an adhesive product having an adhesive microsphere composition ratio of 67% on a predetermined PPC paper (product name KB39N: manufactured by KOKUYO Co., Ltd.) with a thickness of 50 μm. A weight of 200 g in which the shape of the contact portion is a circle of Φ1 and the material is SBR is allowed to stand on the spread adhesive surface 5 seconds after the spread. After 5 seconds, the contact portion is separated from the adhesive surface, and when the contact portion is separated, tack is confirmed, and it is confirmed whether or not the adhesive is attached to the contact portion of the weight.

Regarding the presence or absence of wrinkles on the paper, a bar capable of applying an adhesive product in which the composition ratio of adhesive microspheres is adjusted to 67% on a predetermined PPC paper (product name KB39N: manufactured by KOKUYO Co., Ltd.) with a thickness of 50 μm. The coating was spread using a coater, and one minute after the coating, the state of the PPC paper in the portion where the adhesive was spread was visually confirmed.

<Test results and discussion>
Below, for each Example and Comparative Example 1, the results of carrying out these tests are summarized in a table and shown in FIG.

With respect to Examples 1 to 4, the adhesive strength, the drying property, the presence or absence of wrinkles on the paper, and the suitability as an adhesive were all good. That is, in Examples 1 to 4, the dispersion medium was dried within 10 seconds after application, so that the adhesive was layered on the paper without forming wrinkles on the paper as schematically shown on the left side of FIG. Is applied to. That is, Examples 1 to 4 satisfy the suitability as an adhesive product according to the present invention, in which the coating marks are inconspicuous and the adhesive can be fixed to the object to be fixed. In addition, in this embodiment, the adhesive strength is 0.5 N / cm or more, specifically 2.5 N / cm, 2.0 N / cm, 2.4 N / cm, 2.1 N / cm, as shown in FIG. It is cm, and both are 2.0 N / cm or more. That is, each of these examples shows an excellent value of 1.5 N / cm or more, which is suitable for sealing envelopes for office use, for example.

Then, according to Examples 1 to 4 described above, it is shown that various monomer components can be used and various cross-linking agents can be used in the method for producing the adhesive product according to these Examples by appropriately setting the production conditions. ing.

In Comparative Example 1, the adhesive strength is 0.5 N / cm or more, specifically 1.6 N / cm, which is an excellent value up to more than 1.5 N / cm, which is suitable for sealing envelopes in office use, for example. However, neither the dryness nor the presence or absence of wrinkles of the paper met the required requirements, resulting in lack of suitability as an adhesive. In Comparative Example 1, as shown on the left side of FIG. 10, wrinkles were formed on the paper. It is considered that this is because the content of water in the dispersion medium is higher than 6%. Therefore, it is probable that the dispersion medium did not dry after application and remained for a long time of 10 seconds or more, so that water permeated into the inside of the paper and wrinkles were formed.

The present invention can be used as an adhesive product that can be applied as a glue product for fixing paper.

A ... Adhesive product AL ... Dispersion medium (alcohol)
G ... Adhesive P ... Polymer, polymer component (polymer)
CP ... Copolymer
M ... Monomer, monomer component (monomer)
B ... Cross-linking agent Z ... Reaction initiator ST ... Dispersion stabilizer Q ... Additive additive IG ... Inert gas PA ... Paper W ... Wrinkles S1 ... Preparation step S2 ... Start step (reaction start step)
S3 ... Polymerization step S4 ... Adjustment step

Claims (7)

And a dispersion medium alcohol content of 2 to 4 carbon atoms containing less than 1% by weight and and water 99 wt% or more, the pressure-sensitive adhesive composition for constituting the dispersed such Rineba Chakuzai in the dispersion medium Stored in a container having a head portion that includes a substance, contains 25 to 45 parts by weight of a dispersion medium, and 55 to 75 parts by weight of the adhesive, and can be applied little by little to the paper to be applied. The pressure-sensitive adhesive composition is dispersed in a dispersion medium in a polymer state to form an emulsion .
Under the condition that the adhesive strength of the adhesive material conforms to JIS Z 0237-8, the composition ratio of the adhesive material composition is adjusted to 67%, and the adhesive material is coated on a corona-treated PET film with a thickness of 50 μm. After leaving it for 1 minute to volatilize the dispersion medium, it is processed into a strip of 10 mm x 150 mm, attached to a stainless steel plate treated according to JIS Z 0237-8, and 5 mm / s with a 2 kg kg roller. × 1 It must be 2.0 N / cm or more when the peeling resistance is measured at a speed of 300 mm / min by Autograph (registered trademark) (manufactured by Shimadzu Corporation) after 40 minutes. Adhesive products featuring. The pressure-sensitive adhesive product according to claim 1, wherein the pressure-sensitive adhesive composition formed in the dispersion medium has an average particle size of 0.1 to 10 μm. The pressure-sensitive adhesive product according to claim 1 or 2 , wherein the pressure-sensitive adhesive comprises the pressure-sensitive adhesive composition and a function-imparting agent for imparting a specific function. The pressure-sensitive adhesive product according to claim 1, 2 or 3, wherein the pressure-sensitive adhesive composition is a polymer and / or a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms. Alcohol content of 2 to 4 carbon atoms is dispersed a viscous Chakuzai in a dispersion medium containing less than 1% by weight and and water 99 wt% or more, so that can be applied in small amounts to the paper is coated object A pressure-sensitive adhesive product that is stored in a container having a head portion and is used to produce a pressure-sensitive adhesive product in which the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive is dispersed in a dispersion medium in a polymer state to form an emulsion. It is a manufacturing method of
A preparatory step of dissolving a monomer component and a cross-linking agent, which are raw materials for the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive, in the dispersion medium.
A start step of subjecting the dispersion medium, the monomer component, and the cross-linking agent in the preparation step to a reaction start treatment, and
A polymerization step of proceeding with the polymerization and cross-linking of the monomer component in the starting step to obtain the pressure-sensitive adhesive composition which is a polymer and / or a copolymer in which the monomer component is dispersed in the dispersion medium.
After the polymerization step, there is an adjustment step of adjusting the amount of the dispersion medium so that the dispersion medium is 25 to 45 parts by weight and the pressure-sensitive adhesive is 55 to 75 parts by weight .
Under the condition that the adhesive strength of the adhesive material conforms to JIS Z 0237-8, the composition ratio of the adhesive material composition is adjusted to 67%, and the adhesive material is coated on a corona-treated PET film with a thickness of 50 μm. After leaving it for 1 minute to volatilize the dispersion medium, it is processed into a strip of 10 mm x 150 mm, attached to a stainless steel plate treated according to JIS Z 0237-8, and 5 mm / s with a 2 kg kg roller. × 1 It must be 2.0 N / cm or more when the peeling resistance is measured at a speed of 300 mm / min by Autograph (registered trademark) (manufactured by Shimadzu Corporation) after 40 minutes. A method for manufacturing an adhesive product. The method for producing a pressure-sensitive adhesive product according to claim 5, wherein the adjustment step comprises a procedure of forming the pressure-sensitive adhesive together with the pressure-sensitive adhesive composition and adding a function-imparting agent for imparting a specific function to the pressure-sensitive adhesive. The difference in SP value between the dispersion medium and the monomer component is ^{less than 6.5 (MPa) 1/2} , and the difference in SP value between the dispersion medium and the polymer and / or copolymer is 6. The method for producing an adhesive product according to claim 5 or 6, which is 5 (MPa) ^{1/2 or more.}

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