JP2006008925A - Transparent pressure-sensitive adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent pressure-sensitive adhesive composition excellent in transparency and pressure-sensitive adhesiveness and useful for a material for a kneaded eraser and a pressure-sensitive adhesive material, etc. <P>SOLUTION: This transparent pressure-sensitive adhesive composition comprises a styrene type elastomer and a transparent rubber. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent pressure-sensitive adhesive composition, and more particularly, to a transparent pressure-sensitive adhesive composition that is transparent and excellent in pressure-sensitive adhesive properties, and is useful as a kneading and pressure-sensitive adhesive material.

  Conventionally, as this type of transparent composition, a composition mainly composed of a vinyl chloride resin is known.

  For example, a vinyl chloride resin for paste having an average degree of polymerization exceeding 800 and a residual amount of emulsifier of 0.5% by weight or less and a plasticizer having a refractive index of 1.50 to 1.60 as main components. There has been proposed a vinyl chloride resin character eraser with excellent transparency, which is characterized by, for example (see Patent Document 1).

Moreover, 60-200 weight part of BBP as a plasticizer is added to 100 weight part of paste vinyl chloride resin which contains a phosphoric acid ester type emulsifier, and is produced by emulsion polymerization with a polymerization degree of 2300-2600, and a tin compound, Ba-Zn series A paste vinyl chloride resin composition comprising 0.1 to 5 parts by weight of a stabilizer selected from a compound, a Ca—Zn compound and a mixture thereof has been proposed (see, for example, Patent Document 2).
Japanese Patent Application Laid-Open No. 60-242098 Japanese Examined Patent Publication No. 63-49640

  However, compositions containing these vinyl chloride resins as a main component include a problem of migration.

  On the other hand, in recent years, demands from customers have also diversified in the field of erasing, and there is a demand for transparent erasing rich in decoration, hobby, and playability. However, the conventional kneading contains a sub, so that it is impossible to make the whole dough transparent.

  In addition, since the base resin itself is required to have transparency, there is a problem that the degree of freedom in resin selection is narrow. For example, butadiene rubber, vinyl acetate resin, acrylic resin, olefin-based elastomer, styrene-based elastomer, and the like can be considered as transparent resins, but all have a drawback that they do not have sufficient elongation.

  On the other hand, rubbers such as natural rubber and butyl rubber are excellent in elongation and re-adhesion of the fabric, but are somewhat inferior in transparency and inadequate in shape retention against heat.

  The present invention provides a transparent adhesive composition that solves the problems of the prior art, has excellent transparency and adhesiveness, has sufficient elongation and shape retention for heat, and is useful as a kneading or adhesive material. Is.

  As a result of intensive studies to solve the above problems, the present inventors have used a styrene-based elastomer, and preferably, by adding a transparent rubber to this, it has excellent transparency and adhesiveness, sufficient elongation and The inventors have found that a composition having shape retaining property against heat and useful as a kneading agent or an adhesive material can be obtained, and the present invention has been completed.

  That is, claim 1 of the present invention includes a transparent pressure-sensitive adhesive composition characterized by adding a transparent rubber to a styrene-based elastomer.

  Claim 2 of the present invention includes the transparent adhesive composition according to claim 1, wherein the transparent rubber is selected from natural rubber, isoprene rubber, and butyl rubber.

  The third aspect of the present invention includes the transparent adhesive composition according to the first or second aspect, further comprising a softener.

  Claim 4 of the present invention includes the transparent adhesive composition according to claim 3, wherein the softening agent comprises process oil.

  The fifth aspect of the present invention includes the transparent adhesive composition according to any one of the first to fourth aspects, further comprising a filler. .

  Claim 6 of the present invention is the transparent adhesive composition according to any one of claims 1 to 5, wherein the addition amount of the transparent rubber is 5 to 100 parts by weight with respect to 100 parts by weight of the styrene elastomer. Content.

  According to a seventh aspect of the present invention, the addition amount of the softening agent is 70 to 130 parts by weight with respect to 100 parts by weight of the styrene elastomer and the transparent rubber. The transparent tackiness according to any one of claims 3 to 6 The composition is the content.

  Claim 8 of the present invention is the transparent adhesive composition according to any one of claims 5 to 7, wherein the filler is added in an amount of 10 parts by weight or less based on 100 parts by weight of the styrene elastomer and the transparent rubber. The thing is the content. .

  Claim 9 of the present invention is a paste, and contains the transparent adhesive composition according to any one of claims 1 to 8.

  Claim 10 of this invention is an adhesive material, The content is the transparent adhesive composition of any one of Claims 1-8.

  The eleventh aspect of the present invention includes a transparent adhesive having a styrene elastomer having a tensile elongation at break of 100% or less and a melt flow rate (230 ° C., 2.16 kg) of 1 g / 10 min or less. The composition is the content.

  The twelfth aspect of the present invention is that a transparent rubber is added to a styrene elastomer having a tensile elongation at break of 100% or less and a melt flow rate (230 ° C., 2.16 kg) of 1 g / 10 min or less. Item 11. The transparent adhesive composition according to Item 11 is included.

  Claim 13 of the present invention contains the transparent adhesive composition according to claim 12, wherein the transparent rubber is selected from natural rubber, isoprene rubber, and butyl rubber.

  A fourteenth aspect of the present invention includes the transparent adhesive composition according to any one of the eleventh to thirteenth aspects, further comprising a softening agent.

  A fifteenth aspect of the present invention includes the transparent adhesive composition according to the fourteenth aspect, wherein the softening agent is a process oil.

  A sixteenth aspect of the present invention includes the transparent adhesive composition according to any one of the eleventh to fifteenth aspects, further comprising a filler.

  Claim 17 of the present invention is the transparent adhesive composition according to any one of claims 12 to 16, wherein the addition amount of the transparent rubber is 5 to 100 parts by weight with respect to 100 parts by weight of the styrene elastomer. Content.

  Claim 18 of the present invention is the transparent adhesive property according to any one of claims 14 to 17, wherein the addition amount of the softening agent is 70 to 130 parts by weight with respect to 100 parts by weight of the styrene elastomer and the transparent rubber. The composition is the content.

  The transparent adhesive composition according to any one of claims 16 to 18, wherein the filler is added in an amount of 10 parts by weight or less based on 100 parts by weight of the styrene elastomer and the transparent rubber. The thing is the content.

  The twentieth aspect of the present invention includes the transparent adhesive composition according to any one of the eleventh to nineteenth aspects, which is a paste.

  Claim 21 of the present invention is an adhesive material, comprising the transparent adhesive composition according to any one of claims 11 to 19.

  According to the present invention, by using a styrene-based elastomer that is excellent in transparency but lacks in elongation, preferably, this is combined with a transparent rubber that is slightly inferior in transparency and shape retention against heat but excellent in elongation. Thus, the compatibility is good, both are uniformly dispersed and mixed, and a transparent adhesive composition excellent in transparency and adhesiveness is provided.

  In addition, the transparent pressure-sensitive adhesive composition of the present invention has a sufficient elongation and is excellent in re-adhesiveness when repeatedly kneaded, and can provide a transparent paste having a clean feeling, a clarification feeling, and an interesting property.

  Furthermore, since the transparent adhesive composition of the present invention is non-drying and excellent in transparency and excellent in adhesiveness, it falls down or drops such as glue, thumbtack, furniture in case of earthquake, OA equipment such as computer, printer, etc. It is possible to provide an adhesive material such as an adhesive mat for preventing the above and an adhesive sheet for dust removal rollers.

  The styrene-based elastomer used in the present invention includes Septon 1001 (manufactured by Kuraray Co., Ltd.), Kraton G1701 (manufactured by Kraton Polymer), and styrene-ethylene-propylene-styrene copolymer. Septon 2005, 2006, 2104, 2002 (above, manufactured by Kuraray Co., Ltd.), and styrene-ethylene-butadiene-styrene copolymers include Septon 8006, 8004 (above, Kuraray Co., Ltd.), Examples of Kraton G1651 (manufactured by Kraton Polymer) and styrene-ethylene-ethylene-propylene-styrene copolymer include Septon 4055 and 4077 (manufactured by Kuraray Co., Ltd.).

  The styrenic elastomer preferably has a tensile elongation at break of 100% or less. For example, in the above, Septon 1001, 2104, and Kraton G1701 are <100%, and Septon 2005, 2006, 4055, 4077. 8006 and Kraton G1651 are values that are too small to be measured. In addition, Septon 8004 is 560% and 2002 is 580%.

  Further, the styrene elastomer preferably has a melt flow rate (MFR) (230 ° C., 2.16 kg) of 1 g / 10 min or less, the above-mentioned septon 1001 is 0.1 g / 10 min, and septon 2104 is 0.4 g / min. 10 min, septon 8004 is 0.1 g / 10 min. In addition, Septon 2005, 2006, 4055, 4077, 8006, Clayton G1701 and G1651 have values that are so small that they cannot be measured under the conditions of 230 ° C. and 2.16 kg. The septon 2002 is 70 g / 10 min.

If the tensile elongation at break exceeds 100% or the melt flow rate exceeds 1 g / 10 min, the dough tends to be too firm and, as a result, tends to be difficult to stretch and lack re-adhesiveness. Therefore, Septon 1001, 2005, 2006, 2104, 4055, 4077, 4077, 4077, which have a tensile elongation at break of 100% or less and a melt flow rate (230 ° C., 2.16 kg) of 1 g / 10 min or less. 8006, Kraton G1701, and G1651 are preferable.
The above-mentioned styrenic elastomers are used alone or in combination of two or more as required.
In the present invention, the tensile elongation at break is measured according to JIS K 6301, and the melt flow rate (230 ° C., 2.16 kg) is measured according to JIS K 7210.

  In the present invention, a transparent rubber is preferable as a component that imparts elongation to the styrene-based elastomer, and examples of such transparent rubber include natural rubber, isoprene rubber, butyl rubber, polybutene, and the like. 2 or more types are used in combination. In particular, natural rubber, isoprene rubber, and butyl rubber are preferable. The transparent rubber in the present invention can be used as long as it has transparency even if it is colored.

  Examples of natural rubber include RSS No. 1, and examples of isoprene rubber include Kraton IR305 (manufactured by Kraton). Examples of the butyl rubber include Exxon Butyl 268, Vistanex MML80, Vistanex MML140 (exxon).

  The addition amount of the transparent rubber varies depending on the type of the transparent rubber and the use of the composition of the present invention, so it cannot be determined unconditionally. For example, in the case of kneading, usually 100 weight of styrene elastomer 5-100 weight part is preferable with respect to a part. If the amount is less than 5 parts by weight, the elongation tends to be insufficient. On the other hand, if the amount exceeds 100 parts by weight, the elongation is not preferable because a strong force is required.

A softener is usually added to the composition of the present invention. The softener, together with the transparent rubber, imparts elongation and re-adhesion to a styrene elastomer having a low tensile elongation at break and a low melt flow rate. As such a softening agent, either mineral oil or vegetable oil can be used, and process oil is particularly suitable. Examples of the process oil include paraffinic oil and naphthenic oil, and the former includes PW32 and the latter includes NP24 (both manufactured by Idemitsu Kosan Co., Ltd.). These may be used alone or in combination as necessary.
The addition amount of the softening agent is usually 70 to 130 parts by weight with respect to 100 parts by weight of the styrene elastomer and the transparent rubber. If it is less than 70 parts by weight, it is hard and the elongation is insufficient. On the other hand, if it exceeds 130 parts by weight, it tends to cause sticky bleeding.

  If necessary, a filler that does not impair the transparency can be added to the composition of the present invention. Examples of such additives include LP-3106 [manufactured by Mitsubishi Rayon, acrylic (PMMA) powder], nip seal VN-3 [manufactured by Tosoh, silica (wet method white carbon)] and the like. These are used alone or in combination as necessary, and the amount used is preferably about 10 parts by weight or less based on 100 parts by weight of the styrene elastomer and the transparent rubber. If it exceeds 10 parts by weight, it tends to become cloudy. Furthermore, if necessary, an angstrom-level fine oxide, for example, indium oxide, iron oxide, tin oxide, titanium oxide, barium sulfate, etc. can be added for the purpose of imparting conductivity or cutting ultraviolet rays. .

  The transparent adhesive composition of the present invention comprising the above components is kneaded, molded by press molding, injection molding, extrusion molding, or the like, and cut into a predetermined size to obtain a product.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, these do not restrict | limit the scope of the present invention at all.

  The materials used in the following examples and comparative examples are shown in Table 1. In addition, in description of Table 2-Table 8, unless otherwise indicated, a compounding part number represents a weight part.

Examples 1-4, Comparative Example 1
As shown in Table 2, after mixing and mixing a resin composition containing “Septon 8006” as a thermoplastic elastomer, butyl rubber “Vistanex MML80” as a transparent rubber, and process oil “PW32” as a softening agent, extrusion molding A sample was obtained.
About the obtained sample, transparency, elongation, and shape retention during heating were evaluated by the following methods. The results are shown in Table 2.

"Transparency"
Samples were evaluated with the naked eye and evaluated according to the following criteria.
A: The transparency is very high.
○: High transparency.

"Elongation"
The sample was stretched with both hands, and the degree of elongation was evaluated according to the following criteria.
A: It grows very well.
○: It grows well.
□: Elongates but easily cuts.
Δ: Although it is stretched, a considerable force is required.
X: Not stretched.

"Shape retention"
The sample was stored in a constant temperature bath at 70 ° C. for a certain period, and shape retention was evaluated with the naked eye according to the following criteria.
A: Retain shape until 4 weeks.
○: Retain shape until 3 weeks.
Δ: Retain shape until 2 weeks.

Examples 5-8
As shown in Table 3, physical properties were evaluated in the same manner as in Examples 1 to 4, except that butyl rubber “Vistanex MML140” was used as the transparent rubber. The evaluation results are shown in Table 3. For comparison, the evaluation results of Comparative Example 1 are also shown.

Examples 9-13
As shown in Table 4, physical properties were evaluated in the same manner as in Examples 1 to 4 except that butyl rubber “Exon butyl 268” was used as the transparent rubber. The evaluation results are shown in Table 4. For comparison, the evaluation results of Comparative Example 1 are also shown.

Examples 14-17
As shown in Table 5, physical properties were evaluated in the same manner as in Examples 1 to 4, except that isoprene rubber “Clayton IR305” and natural rubber “RSS No. 1” were used as the transparent rubber. The evaluation results are shown in Table 5.

Examples 18-27
As shown in Table 6, Example 2 was used except that Septon 1001, 2005, 2006, 2104, 4055, 4077, 8004, 2002, Kraton G1651, 1701 were used as the thermoplastic elastomer. The same operation was performed to evaluate the physical properties. The evaluation results are shown in Table 6. For comparison, the evaluation results of Example 2 are also shown.
As is apparent from the results in Table 6, Septon 8004 is a styrene elastomer that does not satisfy the conditions that the tensile elongation at break is 100% or less and the melt flow rate (230 ° C., 2.16 kg) is 1 g / 10 min or less. When the same 2002 is used, it is understood that a considerable force is required although it extends.

Examples 28-32
As shown in Table 7, Examples 28 to 31 were operated in the same manner as Example 2 except that the amount of process oil “PW32” was changed, and the physical properties were evaluated. Table 7 shows the evaluation results. For comparison, the evaluation results of Example 2 are also shown.
In Example 32, process oil “NP24” was used.

Examples 33-36
As shown in Table 8, physical properties were evaluated in the same manner as in Example 2 except that “LP-3106” and “nip seal VN-3” were added as fillers. The evaluation results are shown in Table 8. For comparison, the evaluation results of Example 2 are also shown.

  The samples obtained in the above Examples 1 to 36 were transparent and adhesive, and could be used as an adhesive mat for kneading, preventing overturning or dropping, an adhesive sheet for a dust removal roller, and the like.

  As described above, the transparent pressure-sensitive adhesive composition of the present invention has a sufficient elongation and is excellent in re-adhesiveness when repeatedly kneaded, and can provide a transparent kneading rich in cleanliness, clarity and interest. it can.

Furthermore, since the composition of the present invention is non-drying and excellent in transparency and excellent in adhesiveness, it prevents the fall or fall of OA equipment such as glue, thumbtack, furniture in case of earthquake, computer, printer, etc. Adhesive materials such as an adhesive mat and an adhesive sheet for dust removal rollers can be provided.

Claims (21)

  A transparent adhesive composition comprising a styrene elastomer and a transparent rubber added thereto.   The transparent adhesive composition according to claim 1, wherein the transparent rubber is selected from natural rubber, isoprene rubber, and butyl rubber.   Furthermore, the transparent adhesive composition of Claim 1 or 2 formed by adding a softening agent.   The transparent adhesive composition according to claim 3, wherein the softening agent comprises process oil.   Furthermore, the transparent adhesive composition of any one of Claims 1-4 formed by adding a filler.   The transparent adhesive composition according to any one of claims 1 to 5, wherein the addition amount of the transparent rubber is 5 to 100 parts by weight with respect to 100 parts by weight of the styrene elastomer.   The transparent adhesive composition according to any one of claims 3 to 6, wherein the addition amount of the softening agent is 70 to 130 parts by weight with respect to 100 parts by weight of the styrene elastomer and the transparent rubber.   The transparent adhesive composition according to any one of claims 5 to 7, wherein the filler is added in an amount of 10 parts by weight or less based on 100 parts by weight of the styrene elastomer and the transparent rubber.   The transparent adhesive composition according to any one of claims 1 to 8, wherein the transparent adhesive composition is kneaded.   It is an adhesive material, The transparent adhesive composition of any one of Claims 1-8.   A transparent adhesive composition comprising a styrene elastomer having a tensile elongation at break of 100% or less and a melt flow rate (230 ° C., 2.16 kg) of 1 g / 10 min or less.   The transparent adhesive composition according to claim 11, wherein a transparent rubber is added to a styrene elastomer having a tensile elongation at break of 100% or less and a melt flow rate (230 ° C, 2.16 kg) of 1 g / 10 min or less. object.   The transparent adhesive composition according to claim 12, wherein the transparent rubber is selected from natural rubber, isoprene rubber, and butyl rubber.   Furthermore, the transparent adhesive composition of any one of Claims 11-13 formed by adding a softening agent.   The transparent adhesive composition according to claim 14, wherein the softening agent comprises a process oil.   Furthermore, the transparent adhesive composition of any one of Claims 11-15 formed by adding a filler.   The transparent adhesive composition according to any one of claims 12 to 16, wherein the addition amount of the transparent rubber is 5 to 100 parts by weight with respect to 100 parts by weight of the styrene elastomer.   The transparent adhesive composition according to any one of claims 14 to 17, wherein the addition amount of the softening agent is 70 to 130 parts by weight with respect to 100 parts by weight of the styrene elastomer and the transparent rubber.   The transparent adhesive composition according to any one of claims 16 to 18, wherein an addition amount of the filler is 10 parts by weight or less with respect to 100 parts by weight of the styrene elastomer and the transparent rubber.   The transparent adhesive composition according to any one of claims 11 to 19, which is kneaded. It is an adhesive material, The transparent adhesive composition of any one of Claims 11-19.