JP5658011B2 - Polychloroprene adhesive composition and method for producing the same - Google Patents
Polychloroprene adhesive composition and method for producing the same Download PDFInfo
- Publication number
- JP5658011B2 JP5658011B2 JP2010262443A JP2010262443A JP5658011B2 JP 5658011 B2 JP5658011 B2 JP 5658011B2 JP 2010262443 A JP2010262443 A JP 2010262443A JP 2010262443 A JP2010262443 A JP 2010262443A JP 5658011 B2 JP5658011 B2 JP 5658011B2
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- JP
- Japan
- Prior art keywords
- sulfur
- chloroprene polymer
- modified chloroprene
- adhesive composition
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000001070 adhesive effect Effects 0.000 title claims description 94
- 239000000853 adhesive Substances 0.000 title claims description 93
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 152
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- -1 sulfur modified chloroprene Chemical class 0.000 claims description 52
- 238000006116 polymerization reaction Methods 0.000 claims description 45
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- 239000003960 organic solvent Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
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Description
本発明は、ポリクロロプレン系接着剤組成物及びその製造方法に関する。より詳しくは、ポリクロロプレンを主原料とする接着剤組成物の性能を向上させる技術に関する。 The present invention relates to a polychloroprene adhesive composition and a method for producing the same. More specifically, the present invention relates to a technique for improving the performance of an adhesive composition containing polychloroprene as a main raw material.
クロロプレン系重合体は、耐熱性、耐候性、耐オゾン性、耐薬品性、難燃性（自己消火性）等に優れた物質であり、天然ゴムや他の合成樹脂等と比較しても多くの優れた特性を有する。このように全体的にバランスのとれた物性であるクロロプレン系重合体は、種々の用途に使用されており、その中の代表例として接着剤としての用途が挙げられる。 Chloroprene-based polymers are excellent in heat resistance, weather resistance, ozone resistance, chemical resistance, flame resistance (self-extinguishing), etc., and much more than natural rubber and other synthetic resins. It has excellent characteristics. As described above, chloroprene polymers having balanced physical properties are used in various applications, and typical examples include applications as adhesives.
ポリクロロプレン系接着剤は、トルエンやアセトン等の有機溶剤に、クロロプレン系重合体、粘着付与樹脂及び金属酸化物等を溶解及び／又は分散させたものであり、有機溶剤が揮発することにより硬化・接着する。このポリクロロプレン系接着剤は、初期立ち上り接着強さ等の接着特性に優れていることから、木工、家具及び車両等といった幅広い分野において使用されている（例えば、特許文献１，２参照。）。 A polychloroprene adhesive is a solution obtained by dissolving and / or dispersing a chloroprene polymer, a tackifying resin, a metal oxide, or the like in an organic solvent such as toluene or acetone. Glue. This polychloroprene adhesive is excellent in adhesive properties such as initial rising adhesive strength, and is therefore used in a wide range of fields such as woodwork, furniture and vehicles (see, for example, Patent Documents 1 and 2).
一方、クロロプレン系接着剤は、貯蔵している間に、「層分離」が発生しやすく、従来、耐層分離性に優れたクロロプレン系重合体組成物が提案されている（例えば、特許文献３，４参照。）。特許文献３，４に記載の組成物では、クロロプレンをロジン酸及び／又はロジン酸塩の存在下で重合体した後、特定のエチレン性不飽和スルホン酸化合物を添加したり、熱処理したりすることで、層分離安定性向上を図っている。 On the other hand, chloroprene-based adhesives are prone to “layer separation” during storage, and conventionally, chloroprene-based polymer compositions having excellent layer separation resistance have been proposed (for example, Patent Document 3). , 4). In the compositions described in Patent Documents 3 and 4, chloroprene is polymerized in the presence of rosin acid and / or rosinate, and then a specific ethylenically unsaturated sulfonic acid compound is added or heat-treated. Therefore, the layer separation stability is improved.
しかしながら、前述した特許文献３，４に記載されている従来のポリクロロプレン系接着剤組成物は、耐層分離性及び耐熱接着力が十分に得られないという問題点がある。 However, the conventional polychloroprene adhesive compositions described in Patent Documents 3 and 4 described above have a problem that the layer separation resistance and the heat resistant adhesive force cannot be sufficiently obtained.
そこで、本発明は、耐熱接着力及び耐層分離性に優れたポリクロロプレン系接着剤組成物及びその製造方法を提供することを主目的とする。 Accordingly, the main object of the present invention is to provide a polychloroprene adhesive composition excellent in heat-resistant adhesive strength and delamination resistance and a method for producing the same.
本発明者は、前述した問題を解決すべく鋭意検討を行った結果、硫黄変性していないクロロプレン系重合体に硫黄変性クロロプレン系重合体をブレンドすることにより、優れた耐熱接着力を維持しつつ、耐層分離性を向上できることを見出し、本発明に至った。 The present inventor has conducted intensive studies to solve the problems described above, by blending the sulfur-modified chloroprene polymer in the chloroprene polymer which is not sulfur-modified, while maintaining excellent heat adhesion The inventors have found that the layer separation resistance can be improved, and have reached the present invention.
即ち、本発明に係るポリクロロプレン系接着剤組成物は、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して得た非硫黄変性クロロプレン系重合体と、硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して得た硫黄変性クロロプレン系重合体と、有機溶剤と、を含有し、前記非硫黄変性クロロプレン系重合体及び前記硫黄変性クロロプレン系重合体が、前記有機溶剤中に溶解しているものである。
この接着剤組成物では、前記硫黄変性クロロプレン系重合体として、単量体１００質量部に対して、硫黄の量を０．０１〜２．５質量部として重合したものであり、重合率が５０％以上であるものを使用することができる。
また、前記非硫黄変性クロロプレン系重合体及び前記硫黄変性クロロプレン系重合体には、乳化剤としてロジン酸及び／又はロジン酸の金属塩を使用し、単量体１００質量部あたりの乳化剤量を０．５〜７．０質量部として乳化重合したものとしてもよい。
更に、前記硫黄変性クロロプレン系重合体は、チウラム化合物を０．３〜６．０質量％含有していてもよい。
更にまた、前記非硫黄変性クロロプレン系重合体と前記硫黄変性クロロプレン系重合体の配合比は、例えば、質量比で、９９：１〜６０：４０とすることができる。
更にまた、前記有機溶剤は、トルエン、ベンゼン及びキシレンを含有しないことが望ましい。
更にまた、金属酸化物及び／又は老化防止剤を含有していてもよく、その場合、前記金属酸化物としては、例えば粒子径が３００ｎｍ以下の酸化亜鉛を使用することができる。
That is, the polychloroprene adhesive composition according to the present invention comprises a non-sulfur modified chloroprene polymer obtained by polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene, and sulfur. A sulfur-modified chloroprene polymer obtained by polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene and an organic solvent in the presence of the non-sulfur-modified chloroprene. The polymer and the sulfur-modified chloroprene polymer are dissolved in the organic solvent.
In this adhesive composition, the sulfur-modified chloroprene polymer is polymerized with the amount of sulfur being 0.01 to 2.5 parts by mass with respect to 100 parts by mass of the monomer, and the polymerization rate is 50. % Or more can be used.
The non-sulfur-modified chloroprene polymer and the sulfur-modified chloroprene polymer use rosin acid and / or a metal salt of rosin acid as an emulsifier, and the amount of the emulsifier per 100 parts by mass of the monomer is 0.00. It may be emulsion-polymerized as 5 to 7.0 parts by mass.
Furthermore, the sulfur-modified chloroprene polymer may contain 0.3 to 6.0% by mass of a thiuram compound.
Furthermore, the compounding ratio of the non-sulfur modified chloroprene polymer and the sulfur modified chloroprene polymer can be, for example, 99: 1 to 60:40 by mass ratio.
Furthermore, it is desirable that the organic solvent does not contain toluene, benzene and xylene.
Furthermore, a metal oxide and / or an anti-aging agent may be contained. In that case, as the metal oxide, for example, zinc oxide having a particle diameter of 300 nm or less can be used.
本発明に係るポリクロロプレン系接着剤組成物の製造方法は、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して非硫黄変性クロロプレン系重合体を得る工程と、硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して硫黄変性クロロプレン系重合体を得る工程と、有機溶剤に、前記非硫黄変性クロロプレン系重合体及び前記硫黄変性クロロプレン系重合体を溶解する工程と、を有する。
この接着剤組成物の製造方法では、前記硫黄変性クロロプレン系重合体を得る工程において、単量体１００質量部に対して、硫黄の量を０．０１〜２．５質量部として、重合率が５０％以上になるまで重合してもよい。
また、前記非硫黄変性クロロプレン系重合体を得る工程及び前記硫黄変性クロロプレン系重合体を得る工程は、乳化剤としてロジン酸及び／又はロジン酸の金属塩を使用し、単量体１００質量部あたりの乳化剤量を０．５〜７．０質量部として乳化重合することもできる。
更に、前記非硫黄変性クロロプレン系重合体と前記硫黄変性クロロプレン系重合体とを、それぞれを個別に仕上げて乾燥処理を行った後、シート状又はチップ状にしたものを、混合して有機溶剤に溶解してもよい。
更にまた、前記非硫黄変性クロロプレン系重合体と、前記硫黄変性クロロプレン系重合体と、金属酸化物及び老化防止剤のうちの少なくとも一方とを、前記有機溶剤に直接添加して溶解及び分散させることもできる。
The method for producing a polychloroprene adhesive composition according to the present invention comprises a step of polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene to obtain a non-sulfur- modified chloroprene polymer. A step of polymerizing chloroprene alone in the presence of sulfur or copolymerizing two or more monomers containing chloroprene to obtain a sulfur-modified chloroprene-based polymer, and an organic solvent containing the non-sulfur-modified chloroprene-based polymer. And a step of dissolving the polymer and the sulfur-modified chloroprene polymer.
In the method for producing the adhesive composition, in the step of obtaining the sulfur-modified chloroprene polymer, the amount of sulfur is 0.01 to 2.5 parts by mass with respect to 100 parts by mass of the monomer, and the polymerization rate is You may superpose | polymerize until it becomes 50% or more.
The step of obtaining the non-sulfur-modified chloroprene polymer and the step of obtaining the sulfur-modified chloroprene polymer use rosin acid and / or a metal salt of rosin acid as an emulsifier. Emulsion polymerization can also be carried out with the amount of emulsifier being 0.5 to 7.0 parts by mass.
Further, the non-sulfur-modified chloroprene polymer and the sulfur-modified chloroprene polymer are individually finished and dried, and then mixed into an organic solvent by mixing a sheet or chip. It may be dissolved.
Furthermore, the non-sulfur-modified chloroprene polymer, the sulfur-modified chloroprene polymer, and at least one of a metal oxide and an antioxidant are added directly to the organic solvent and dissolved and dispersed. You can also.
本発明によれば、非硫黄変性クロロプレン系重合体に、硫黄変性クロロプレン系重合体を配合しているため、優れた耐熱接着強度を維持しつつ、耐層分離性を向上させることができる。 According to the present invention, since the sulfur-modified chloroprene polymer is blended with the non-sulfur-modified chloroprene polymer, the layer separation resistance can be improved while maintaining excellent heat-resistant adhesive strength.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
本発明の実施形態に係るクロロプレン系接着剤組成物は、硫黄変性していないクロロプレン系重合体Ａと、硫黄変性クロロプレン系重合体Ｂとを、有機溶剤中に溶解したものである。ここで、「クロロプレン系重合体」とは、２−クロロ−１，３−ブタジエン（クロロプレン）の単独重合体、又は、クロロプレンを含む２種以上の単量体を共重合して得た共重合体をいう。 The chloroprene adhesive composition according to the embodiment of the present invention is obtained by dissolving a chloroprene polymer A that is not sulfur-modified and a sulfur-modified chloroprene polymer B in an organic solvent. Here, the “chloroprene-based polymer” is a copolymer obtained by copolymerizing a homopolymer of 2-chloro-1,3-butadiene (chloroprene) or two or more monomers containing chloroprene. Refers to coalescence.
［非硫黄変性クロロプレン系重合体Ａ］
非硫黄変性クロロプレン系重合体Ａは、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合することにより得られる。その際、クロロプレン単量体と共重合する他の単量体は、１種類に限定されるものではなく、クロロプレンの他に２種以上の単量体を使用することもできる。
[ Non-sulfur modified chloroprene polymer A]
The non-sulfur-modified chloroprene polymer A is obtained by polymerizing chloroprene alone or by copolymerizing two or more monomers containing chloroprene. In that case, the other monomer copolymerized with the chloroprene monomer is not limited to one type, and two or more types of monomers can be used in addition to chloroprene.
その種類は特に限定されるものではないが、例えばアクリル酸メチル、アクリル酸ブチル及びアクリル酸２−エチルヘキシル等のアクリル酸のエステル類、メタクリル酸メチル、メタクリル酸ブチル及びメタクリル酸２−エチルヘキシル等のメタクリル酸のエステル類、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシメチル（メタ）アクリレート及び２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ（メタ）アクリレート類、２，３−ジクロロ−１，３−ブタジエン、１−クロロ−１，３−ブタジエン、ブタジエン、イソプレン、エチレン、スチレン並びにアクリロニトリル等を用いることができる。 The type is not particularly limited, but for example, esters of acrylic acid such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and methacrylates such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. Acid esters, 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate and hydroxy (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2,3-dichloro-1,3- Butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, ethylene, styrene, acrylonitrile, and the like can be used.
非硫黄変性クロロプレン系重合体Ａの最終重合率は、所望するポリクロロプレン系接着剤組成物の物性や用途等を考慮して、適宜決定することができるが、最終重合率が５０％未満の場合、接着剤組成物の接着強度が低くなりすぎることがある。このため、非硫黄変性クロロプレン系重合体Ａの最終重合率は、５０％以上であることが好ましく、より好ましくは６０〜９５％、更に好ましくは６２〜８２％である。これにより、適度な接着性が得られ、かつ、接着剤の溶液粘度やムーニー粘度の調整が容易になる。 The final polymerization rate of the non-sulfur-modified chloroprene-based polymer A can be determined as appropriate in consideration of the physical properties and applications of the desired polychloroprene-based adhesive composition, but the final polymerization rate is less than 50%. The adhesive strength of the adhesive composition may become too low. For this reason, it is preferable that the final polymerization rate of the non-sulfur modified chloroprene polymer A is 50% or more, more preferably 60 to 95%, still more preferably 62 to 82%. Thereby, moderate adhesiveness is obtained, and adjustment of the solution viscosity and Mooney viscosity of the adhesive becomes easy.
［硫黄変性クロロプレン系重合体Ｂ］
硫黄変性クロロプレン系重合体Ｂは、硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合することにより得られる。その際、クロロプレン単量体と共重合する他の単量体は、前述した非硫黄変性クロロプレン系重合体Ａと同様の単量体を使用することができ、また、この他の単量体は、１種類に限定されるものではなく、２種以上の単量体を併用することもできる。
[Sulfur modified chloroprene polymer B]
The sulfur-modified chloroprene polymer B is obtained by polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene in the presence of sulfur. At that time, as the other monomer copolymerized with the chloroprene monomer, the same monomer as the non-sulfur-modified chloroprene polymer A described above can be used. It is not limited to one type, and two or more types of monomers can be used in combination.
硫黄変性クロロプレン系重合体Ｂの最終重合率は、特に限定されるものではないが、生産性を考慮すると５０％以上とすることが好ましく、６０〜９５％とすることがより好ましい。なお、最終重合率が９５％を超えると、硫黄変性クロロプレン系重合体Ｂの絡み合い分子構造がより複雑になるため、ゲル化して溶剤に溶け難くなることがある。 The final polymerization rate of the sulfur-modified chloroprene polymer B is not particularly limited, but is preferably 50% or more and more preferably 60 to 95% in consideration of productivity. If the final polymerization rate exceeds 95%, the entangled molecular structure of the sulfur-modified chloroprene polymer B becomes more complicated, and may gelate and become difficult to dissolve in a solvent.
また、硫黄変性クロロプレン系重合体Ｂは、分子量調整剤としてチウラム化合物を含有する場合がある。しかしながら、硫黄変性クロロプレン系重合体Ｂにおけるチウラム化合物含有量が０．３質量％未満の場合、添加効果が十分に得られず、粘度調整が難しくなる。一方、チウラム化合物含有量が６．０質量％を超えると、接着剤組成物としたときの貯蔵安定性が低下する。よって、チウラム化合物含有量は、０．３〜６．０質量％であることが望ましい。 The sulfur-modified chloroprene polymer B may contain a thiuram compound as a molecular weight regulator. However, when the thiuram compound content in the sulfur-modified chloroprene polymer B is less than 0.3% by mass, the effect of addition cannot be sufficiently obtained, and viscosity adjustment becomes difficult. On the other hand, when the thiuram compound content exceeds 6.0% by mass, the storage stability of the adhesive composition is lowered. Therefore, the thiuram compound content is desirably 0.3 to 6.0% by mass.
［配合比］
非硫黄変性クロロプレン系重合体Ａと硫黄変性クロロプレン系重合体Ｂの配合比は、特に限定されるものではないが、質量比で、非硫黄変性クロロプレン系重合体Ａ：硫黄変性クロロプレン系重合体Ｂ＝９９：１〜６０：４０とすることが好ましい。クロロプレン系重合体全量あたり硫黄変性クロロプレン系重合体Ｂの量が１質量％未満の場合、接着剤組成物の耐熱接着力及び耐層分離性が不十分となることがある。また、硫黄変性クロロプレン系重合体Ｂの量が４０質量％を超えると、接着剤組成物の貯蔵安定性が低下することがある。
[Combination ratio]
The compounding ratio of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B is not particularly limited, but the mass ratio is non-sulfur-modified chloroprene polymer A: sulfur-modified chloroprene polymer B. = 99: 1 to 60:40 is preferable. When the amount of the sulfur-modified chloroprene polymer B is less than 1% by mass based on the total amount of the chloroprene polymer, the heat resistant adhesive force and the layer separation resistance of the adhesive composition may be insufficient. Moreover, when the amount of the sulfur-modified chloroprene polymer B exceeds 40% by mass, the storage stability of the adhesive composition may be lowered.
［有機溶剤］
前述したクロロプレン系重合体を溶解させる有機溶剤としては、例えば、トルエン、キシレン、アセトン、メチルエチルケトン（ＭＥＫ）、ｎ−ヘキサン、シクロヘキサン、メチルシクロヘキサン、シクロペンタン、酢酸イソプロピル及び酢酸エチル等を使用することができる。また、これの有機溶剤は、単独で使用しても、混合溶剤として使用してもよい。なお、本実施形態のクロロプレン系接着剤組成物では、シックハウス症候群の原因化学物質とされるトルエン、ベンゼン及びキシレン以外の有機溶剤を使用することが望ましく、混合溶剤の場合もこれらを含まないものとすることが望ましい。
[Organic solvent]
Examples of the organic solvent for dissolving the chloroprene polymer include toluene, xylene, acetone, methyl ethyl ketone (MEK), n-hexane, cyclohexane, methylcyclohexane, cyclopentane, isopropyl acetate, and ethyl acetate. it can. These organic solvents may be used alone or as a mixed solvent. In the chloroprene-based adhesive composition of the present embodiment, it is desirable to use an organic solvent other than toluene, benzene and xylene, which is a chemical substance causing sick house syndrome, and even a mixed solvent does not contain these. It is desirable to do.
［その他の添加成分］
本実施形態のポリクロロプレン系接着剤組成物には、前述した各成分に加えて、金属酸化物及び／又は老化防止剤が配合されていてもよい。例えば、金属酸化物を添加すると、接着剤の貯蔵安定性及び接着力を向上させる効果が得られる。本実施形態の接着剤組成物に添加される金属酸化物としては、例えば酸化亜鉛（亜鉛華）、酸化アルミニウム、酸化チタン及び酸化マグネシウム等が挙げられるが、特に、粒子径が３００ｎｍ以下の酸化亜鉛を使用することが望ましい。これにより、接着剤組成物中に分散しやすくなる。
[Other additive components]
In addition to the components described above, the polychloroprene adhesive composition of this embodiment may contain a metal oxide and / or an anti-aging agent. For example, when a metal oxide is added, the effect of improving the storage stability and adhesive strength of the adhesive can be obtained. Examples of the metal oxide added to the adhesive composition of the present embodiment include zinc oxide (zinc white), aluminum oxide, titanium oxide, and magnesium oxide. In particular, zinc oxide having a particle size of 300 nm or less. It is desirable to use Thereby, it becomes easy to disperse | distribute in an adhesive composition.
一方、老化防止剤としては、例えば２，２´−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、２，２´−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，６−ジ−ｔ−ブチル−４−メチルフェノール、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、チオジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ´−ヘキサン−１，６−ジイルビス−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニルプロピオナミド）、３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシアルキルエステル、ジエチル［｛３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル｝メチル］ホスホネート、３，３´，３´´，５，５´，５´´−ヘキサ−ｔ−ブチル−ａ，ａ´，ａ´´−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）ポロピオネート］、４，４´−チオビス（６−ｔ−ブチル−３−メチルフェノール）、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等を用いることができる。 On the other hand, as an anti-aging agent, for example, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,6-diethylene -T-butyl-4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis-3- (3 5-di-t-butyl-4-hydroxyphenylpropionamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester, Ethyl [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl- a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) ) Poropionate], 4,4′-thiobis (6-tert-butyl-3-methylphenol), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, and the like.
また、本実施形態のポリクロロプレン系接着剤組成物には、所望の物性に応じて、粘着付与樹脂、ホルムアルデヒドキャッチャー剤及び充填剤等を添加することもできる。例えば、粘着付与樹脂としては、例えば、フェノール系樹脂、ロジン樹脂、クマロン樹脂及び石油樹脂等を用いることができる。 Moreover, tackifying resin, a formaldehyde catcher agent, a filler, etc. can also be added to the polychloroprene-type adhesive composition of this embodiment according to a desired physical property. For example, as the tackifier resin, for example, phenol resin, rosin resin, coumarone resin, petroleum resin, and the like can be used.
ホルムアルデヒドキャッチャー剤は、有害な揮発性物質であるホルムアルデヒドを捕捉するものであり、例えば、ピロリジン、ピペリジン、ピペラジン、モルホリン、メラミン、ジシアンジアミド、尿素、エチレン尿素、４，５−ジメトキシエチレン尿素、プロピレン尿素、５−メチルプロピレン尿素、５−ヒドロキシプロピレン尿素、５−メトキシプロピレン尿素、オキサリル尿素（パラバン酸）、ヒドラゾベンゾチアゾール、セミカルバジド及びチオセミカルバジド等を用いることができる。 Formaldehyde catcher agent captures formaldehyde, which is a harmful volatile substance, such as pyrrolidine, piperidine, piperazine, morpholine, melamine, dicyandiamide, urea, ethylene urea, 4,5-dimethoxyethylene urea, propylene urea, 5-Methylpropylene urea, 5-hydroxypropylene urea, 5-methoxypropylene urea, oxalyl urea (parabanic acid), hydrazobenzothiazole, semicarbazide, thiosemicarbazide, and the like can be used.
充填剤としては、例えば、タルク、炭酸カルシウム、クレー、スメクタイト、シリカ及びハイドロタルサイトやマイカ等を用いることができる。 As the filler, for example, talc, calcium carbonate, clay, smectite, silica, hydrotalcite, mica and the like can be used.
更に、本実施形態のポリクロロプレン系接着剤組成物には、耐光性を向上させる目的で、ベンゾトリアゾール等の紫外線吸収剤や、ヒンダードアミン等の光安定剤を添加することもできる。 Furthermore, an ultraviolet absorber such as benzotriazole and a light stabilizer such as hindered amine can be added to the polychloroprene adhesive composition of this embodiment for the purpose of improving light resistance.
［製造方法］
次に、本実施形態のポリクロロプレン系接着剤組成物の製造方法について説明する。本実施形態のポリクロロプレン系接着剤組成物の製造方法は、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して非硫黄変性クロロプレン系重合体を得る工程と、硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して硫黄変性クロロプレン系重合体を得る工程と、有機溶剤に、非硫黄変性クロロプレン系重合体及び硫黄変性クロロプレン系重合体を溶解する工程と、を有する。
[Production method]
Next, the manufacturing method of the polychloroprene-type adhesive composition of this embodiment is demonstrated. The production method of the polychloroprene adhesive composition of the present embodiment includes a step of polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene to obtain a non-sulfur-modified chloroprene polymer. under sulfur present, obtaining a sulfur-modified chloroprene polymer of two or more monomers containing or chloroprene polymerizing chloroprene alone copolymerizing, in an organic solvent, non-sulfur-modified chloroprene-based heavy And dissolving the coalesced and sulfur-modified chloroprene polymer.
［重合工程］
非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂを得るための重合反応は、特に限定されるものではなく、乳化重合、塊状重合、懸濁重合及び溶液重合等の公知の方法を適用することができるが、特に乳化重合法が好適である。この乳化重合は、水等を反応溶剤とし、かつ簡便な方法でありながら接着剤として良質なクロロプレン系重合体を得ることができる点で望ましい。即ち、クロロプレン単独又はクロロプレンを含む２種以上の単量体を、乳化剤、分散剤、重合開始剤及び連鎖移動剤等の存在下で、乳化重合させることで、クロロプレン系重合体を得ることができる。
[Polymerization process]
The polymerization reaction for obtaining the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B is not particularly limited, and known methods such as emulsion polymerization, bulk polymerization, suspension polymerization, and solution polymerization are used. Although it can be applied, an emulsion polymerization method is particularly suitable. This emulsion polymerization is desirable in that a high-quality chloroprene polymer can be obtained as an adhesive while using water or the like as a reaction solvent and being a simple method. That is, a chloroprene polymer can be obtained by emulsion polymerization of chloroprene alone or two or more kinds of monomers containing chloroprene in the presence of an emulsifier, a dispersant, a polymerization initiator, a chain transfer agent, and the like. .
また、乳化重合により、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂを得る場合は、乳化剤としてロジン酸及び／又はロジン酸の金属塩を使用することが望ましい。ここで、「ロジン酸」とは、モノカルボン酸系のジテルペン酸であり、分子式Ｃ２０Ｈ３０Ｏ２で表される。本実施形態においては、ロジン酸の異性体については限定されず、例えば、下記化学式１で表されるアビエチン酸、デヒドロアビエチン酸、ジヒドロアビエチン酸、ピマール酸、ジヒドロピマール酸、イソピマール酸及びセコデヒドロアビエチン酸等が挙げられ、これらを単独で使用しても、混合して使用してもよい。なお、乳化剤には、オレイン酸、オクタデセン酸又はステアリン酸等の脂肪酸が含有されていてもよい。 Moreover, when obtaining the non-sulfur modified chloroprene polymer A and the sulfur modified chloroprene polymer B by emulsion polymerization, it is desirable to use rosin acid and / or a metal salt of rosin acid as an emulsifier. Here, “rosinic acid” is a monocarboxylic acid-based diterpenic acid and is represented by the molecular formula C20H30O2. In the present embodiment, the isomers of rosin acid are not limited. For example, abietic acid, dehydroabietic acid, dihydroabietic acid, pimaric acid, dihydropimaric acid, isopimaric acid and secodedehydro represented by the following chemical formula 1 Examples include abietic acid, and these may be used alone or in combination. The emulsifier may contain a fatty acid such as oleic acid, octadecenoic acid or stearic acid.
一方、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの重合工程において使用するロジン酸金属塩は、例えば、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等が挙げられる。これらの中でも、アルカリ金属塩を使用することが望ましく、ナトリウム塩又はカリウム塩を使用することがより望ましい。これにより、取扱い性をより向上させることができる。 On the other hand, examples of the rosin acid metal salt used in the polymerization step of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B include alkali metal salts, alkaline earth metal salts, and ammonium salts. Among these, it is desirable to use an alkali metal salt, and it is more desirable to use a sodium salt or a potassium salt. Thereby, handleability can be improved more.
また、ロジン酸及びロジン酸金属塩の添加量は、クロロプレン系重合体を構成する全単量体１００質量部に対して、ロジン酸及びロジン酸金属塩の総量で０．５〜７．０質量部とすることが好ましい。ロジン酸及びロジン酸金属塩の量が、単量体１００質量部あたり０．５質量部未満の場合、十分な添加効果が得られず、クロロプレンラテックスが不安定となり、重合缶に付着することがある。また、ロジン酸及びロジン酸金属塩の量が、単量体１００質量部あたり７．０質量部を超えると、接着剤組成物としたときに耐層分離性が低下する。なお、ロジン酸及びロジン酸金属塩の添加量は、単量体１００質量部あたり、１．０〜５．０質量部とすることがより好ましい。 The amount of rosin acid and rosin acid metal salt added is 0.5 to 7.0 mass in terms of the total amount of rosin acid and rosin acid metal salt with respect to 100 parts by mass of all monomers constituting the chloroprene polymer. Part. When the amount of rosin acid and rosin acid metal salt is less than 0.5 parts by mass per 100 parts by mass of the monomer, a sufficient addition effect cannot be obtained, and the chloroprene latex may become unstable and adhere to the polymerization can. is there. On the other hand, if the amount of rosin acid and rosin acid metal salt exceeds 7.0 parts by mass per 100 parts by mass of the monomer, the layer separation resistance decreases when an adhesive composition is obtained. In addition, it is more preferable that the addition amount of a rosin acid and a rosin acid metal salt shall be 1.0-5.0 mass parts per 100 mass parts of monomers.
本実施形態においては、重合反応の制御を安定化させるために、適宜、他の乳化剤を併用してもよい。具体的には、芳香族スルホン酸ホルマリン縮合物の金属塩、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウム、アルキルジフェニルエーテルスルホン酸ナトリウム、アルキルジフェニルエーテルスルホン酸カリウム、ポリオキシエチレンアルキルエーテルスルホン酸ナトリウム、ポリオキシプロピレンアルキルエーテルスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテルスルホン酸カリウム及びポリオキシプロピレンアルキルエーテルスルホン酸カリウム等を用いることができる。 In this embodiment, other emulsifiers may be used in combination as appropriate in order to stabilize the control of the polymerization reaction. Specifically, metal salts of aromatic sulfonic acid formalin condensate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium alkyldiphenylethersulfonate, potassium alkyldiphenylethersulfonate, sodium polyoxyethylene alkylethersulfonate, poly Sodium oxypropylene alkyl ether sulfonate, potassium polyoxyethylene alkyl ether sulfonate, potassium polyoxypropylene alkyl ether sulfonate, and the like can be used.
重合反応の重合温度、重合開始剤、連鎖移動剤、重合停止剤及び最終重合率等を適宜、選定・制御することで、重合により得られる非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの分子量、分子量分布、分子末端構造及び結晶化速度等を制御することができる。なお、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂを重合する際の温度は、特に限定されるものではないが、８〜５０℃とすることが好ましく、より好ましくは１０〜４５℃である。重合温度をこの範囲にすることにより、安定的に重合反応を遂行することができる。 By appropriately selecting and controlling the polymerization temperature, polymerization initiator, chain transfer agent, polymerization terminator, final polymerization rate, etc. of the polymerization reaction, the non-sulfur modified chloroprene polymer A and sulfur modified chloroprene heavy polymer obtained by polymerization The molecular weight, molecular weight distribution, molecular terminal structure, crystallization speed, and the like of the combined B can be controlled. The temperature at which the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B are polymerized is not particularly limited, but is preferably 8 to 50 ° C, more preferably 10 to 10 ° C. 45 ° C. By setting the polymerization temperature within this range, the polymerization reaction can be stably performed.
また、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの重合工程において使用される重合開始剤としては、例えば過硫酸カリウム等の無機過酸化物、又はケトンパーオキサイド類、パーオキシケタール類、ハイドロパーオキサイド類、ジアルキルパーオキサイド類及びジアシルパーオキサイド類等の有機化酸化物等が挙げられる。これら重合開始剤の中でも、特に、安定した重合を行なうことができる点から、過硫酸カリウムを使用することが望ましい。 Examples of the polymerization initiator used in the polymerization step of the non-sulfur modified chloroprene polymer A and the sulfur modified chloroprene polymer B include inorganic peroxides such as potassium persulfate, ketone peroxides, peroxy And organic oxides such as ketals, hydroperoxides, dialkyl peroxides and diacyl peroxides. Among these polymerization initiators, potassium persulfate is preferably used from the viewpoint that stable polymerization can be performed.
この重合開始剤の使用条件等については、特に限定されるものではないが、０．１〜５質量％の水溶液として使用することが望ましい。これにより、安定した乳化重合を行うことができる。そして、この重合開始剤を添加することにより、重合反応が開始され、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂが生成する。 The conditions for using this polymerization initiator are not particularly limited, but it is preferably used as a 0.1 to 5% by mass aqueous solution. Thereby, stable emulsion polymerization can be performed. And by adding this polymerization initiator, a polymerization reaction is started, and a non-sulfur modified chloroprene polymer A and a sulfur modified chloroprene polymer B are produced.
更に、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの重合工程では、前述した重合開始剤の活性をより向上させるために、重合促進剤等の添加剤を使用することができる。この重合促進剤（添加剤）としては、例えば、亜硫酸ナトリウム、亜硫酸水素ナトリウム、亜硫酸カリウム、ピロ亜硫酸カリウム、酸化鉄（ＩＩ）、アントラキノンβスルホン酸ナトリウム、ホルムアミジンスルホン酸及びＬ−アスコルビン酸等を用いることができる。 Furthermore, in the polymerization step of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B, additives such as a polymerization accelerator can be used in order to further improve the activity of the polymerization initiator described above. . Examples of the polymerization accelerator (additive) include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium pyrosulfite, iron oxide (II), anthraquinone β sodium sulfonate, formamidine sulfonic acid, and L-ascorbic acid. Can be used.
更にまた、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの重合工程では、連鎖移動剤を用いることもできる。この連鎖移動剤の種類は特に限定されるものではく、例えば、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン及びｎ−オクチルメルカプタン等の長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィド及びジエチルキサントゲンジスルフィド等のジアルキルキサントゲンジスルフィド類、テトラエチルチウラムスルフィド、テトラブチルチウラムスルフィド及びテトラメチルチウラムジスルフィド等のチウラム化合物、又はヨードホルム等を用いることができる。 Furthermore, a chain transfer agent can also be used in the polymerization step of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B. The type of the chain transfer agent is not particularly limited, and examples thereof include long-chain alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and n-octyl mercaptan, and dialkylxanthogens such as diisopropylxanthogen disulfide and diethylxanthogen disulfide. Disulfides, thiuram compounds such as tetraethylthiuram sulfide, tetrabutylthiuram sulfide and tetramethylthiuram disulfide, or iodoform can be used.
なお、硫黄変性クロロプレン系重合体Ｂは、前述した連鎖移動剤を使用して分子量を調整することもできるが、連鎖移動剤を使用せずに重合し、その後の可塑化工程にて分子量を調整することもできる。例えば、連鎖移動剤を使用しないで重合する場合、クロロプレンと硫黄が共重合し、極度の高分子量のポリマーに成長する。そこで、「可塑化工程」において、チウラム化合物等を使用して、この共重合ポリマー中のポリスルフィド結合を化学的に切断し、重合体の分子量を調整する。 The sulfur-modified chloroprene-based polymer B can be adjusted in molecular weight using the chain transfer agent described above, but is polymerized without using the chain transfer agent, and the molecular weight is adjusted in the subsequent plasticizing step. You can also For example, when polymerizing without using a chain transfer agent, chloroprene and sulfur are copolymerized to grow to an extremely high molecular weight polymer. Therefore, in the “plasticization step”, a thiuram compound or the like is used to chemically break polysulfide bonds in the copolymer, thereby adjusting the molecular weight of the polymer.
また、硫黄変性クロロプレン系重合体Ｂを重合する際は、クロロプレン単量体１００質量部又はクロロプレン及びクロロプレンと共重合可能な単量体の合計１００質量部に対して、硫黄の添加量を０．０１〜２．５質量部とすることが望ましい。硫黄は、接着剤組成物としたときに、加硫促進剤として作用する。しかしながら、単量体１００質量部あたりの硫黄添加量が０．０１質量部未満の場合、得られる重合体中の硫黄含有量が不足するため、接着剤組成物の耐熱接着力が不十分となることがある。一方、重合時の硫黄添加量が、単量体１００質量部あたり２．５質量部を超えると、重合中に硫黄が析出してしまうことがある。なお、重合時の硫黄添加量のより好適な範囲は、単量体１００質量部あたり、０．１〜１．０質量部である。 Further, when the sulfur-modified chloroprene-based polymer B is polymerized, the amount of sulfur added is 0.1% with respect to 100 parts by mass of the chloroprene monomer or 100 parts by mass of chloroprene and a monomer copolymerizable with chloroprene. It is desirable to set it as 01-2.5 mass parts. Sulfur acts as a vulcanization accelerator when it is used as an adhesive composition. However, when the amount of sulfur added per 100 parts by mass of the monomer is less than 0.01 parts by mass, the sulfur content in the resulting polymer is insufficient, and the heat resistant adhesive strength of the adhesive composition becomes insufficient. Sometimes. On the other hand, if the amount of sulfur added during polymerization exceeds 2.5 parts by mass per 100 parts by mass of the monomer, sulfur may precipitate during the polymerization. In addition, the more suitable range of the sulfur addition amount at the time of superposition | polymerization is 0.1-1.0 mass part per 100 mass parts of monomers.
非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂの重合工程においては、所望の重合率に達した際に重合反応を停止させるが、その際の停止方法は、特に限定されるものではなく、例えば、重合禁止剤を添加する方法や反応温度を変化させる方法等を適用することができる。 In the polymerization step of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B, the polymerization reaction is stopped when a desired polymerization rate is reached, but the stopping method at that time is particularly limited Instead, for example, a method of adding a polymerization inhibitor or a method of changing the reaction temperature can be applied.
その際、重合禁止剤の種類は特に限定されず、例えば、チオジフェニルアミン、Ｎ，Ｎ−ジエチルヒドロキシルアミン、フェノチアジン、ハイドロキノン、ｐ−ｔ−ブチルカテコール、１，３，５−トリヒドロキシベンゼン及びハイドロキノンメチルエーテル等を用いることができる。 In that case, the type of the polymerization inhibitor is not particularly limited, and examples thereof include thiodiphenylamine, N, N-diethylhydroxylamine, phenothiazine, hydroquinone, pt-butylcatechol, 1,3,5-trihydroxybenzene and hydroquinone methyl. Ether or the like can be used.
［後処理工程］
後処理工程では、例えば、スチームフラッシュ法や濃縮法により高温下に曝すことにより、未反応の単量体等を除去する。その後、未反応の単量体等が除去されたクロロプレン系重合体を、酸性度が中性となるように調整する。その際、中和剤としては、例えば、酢酸及びメタクリル酸等の酸性物質の水溶液、苛性ソーダ、水酸化カリウム及び炭酸ソーダ等の塩基性物質の水溶液等を用いることができる。このような後処理により、クロロプレン系重合体のラテックスを得ることができる。
[Post-processing process]
In the post-treatment process, for example, unreacted monomers are removed by exposure to high temperature by a steam flash method or a concentration method. Thereafter, the chloroprene polymer from which unreacted monomers and the like have been removed is adjusted so that the acidity becomes neutral. In this case, as the neutralizing agent, for example, an aqueous solution of an acidic substance such as acetic acid and methacrylic acid, an aqueous solution of a basic substance such as caustic soda, potassium hydroxide, and sodium carbonate can be used. By such post-treatment, a latex of a chloroprene polymer can be obtained.
［可塑化工程］
硫黄変性クロロプレン系重合体Ｂの可塑化工程に使用される分子量調整剤としては、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド（ＴＥＴ）、テトラブチルチウラムジスルフィド、テトラメチルチウラムジスルフィド、テトラキス（２−エチルヘキシル）チウラムジスルフィド及びジペンタメチレンチウラムテトラスルフィド等のチウラム化合物、ジブチルジチオカルバミン酸ソーダ及びジエチルジチオカルバミン酸ソーダ等のチオカルバミン酸塩類を使用することができる。
[Plasticization process]
The molecular weight modifier used in the plasticizing step of the sulfur-modified chloroprene polymer B is tetramethylthiuram disulfide, tetraethylthiuram disulfide (TET), tetrabutylthiuram disulfide, tetramethylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram. Thiuram compounds such as disulfide and dipentamethylene thiuram tetrasulfide, and thiocarbamates such as sodium dibutyldithiocarbamate and sodium diethyldithiocarbamate can be used.
これらの分子量調整剤は、重合終了後のラテックスに、直接添加することができる。その際、分子量調整剤にチウラム化合物を使用する場合には、前述したように、硫黄変性クロロプレン系重合体Ｂ中に、チウラム化合物が０．３〜６．０質量％含有されるように添加することが望ましい。また、チオカルバミン酸塩類を使用する場合には、硫黄変性クロロプレン系重合体Ｂ中の含有量が４．０質量％以下となるように添加することが望ましい。 These molecular weight regulators can be added directly to the latex after the completion of polymerization. At that time, when a thiuram compound is used as the molecular weight modifier, it is added so that the thiuram compound is contained in the sulfur-modified chloroprene polymer B in an amount of 0.3 to 6.0% by mass as described above. It is desirable. Moreover, when using thiocarbamate, it is desirable to add so that content in the sulfur modified chloroprene polymer B may be 4.0 mass% or less.
［仕上げ乾燥工程］
前述した工程を経て得た非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂのラテックスは、凍結凝固や塩析等の方法で仕上げ乾燥処理を行う。その後、必要に応じて、シート状やチップ状等に成型加工してもよい。
[Finish drying process]
The latex of the non-sulfur-modified chloroprene polymer A and the sulfur-modified chloroprene polymer B obtained through the above-described steps is subjected to a finish drying process by a method such as freeze coagulation or salting out. Thereafter, it may be molded into a sheet shape, a chip shape, or the like as necessary.
［溶解工程］
有機溶剤に、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂ等を溶解する方法は、特に限定されるものではなく、公知の技術を使用できる。ただし、接着剤の品質を制御する上では、前述した仕上げ乾燥工程を行った後に、シート状やチップ状となった各ラテックスを混合し、非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂ等の有機物を有機溶剤に溶解すると共に、ラテックス中に含まれる無機物を有機溶媒中に分散させる方法が好ましい。
[Dissolution process]
The method for dissolving the non-sulfur-modified chloroprene polymer A, the sulfur-modified chloroprene polymer B and the like in the organic solvent is not particularly limited, and a known technique can be used. However, in order to control the quality of the adhesive, after performing the above-described finish drying step, each latex in the form of a sheet or chip is mixed, and the non-sulfur modified chloroprene polymer A and the sulfur modified chloroprene heavy polymer are mixed. A method in which an organic substance such as the combined B is dissolved in an organic solvent and an inorganic substance contained in the latex is dispersed in the organic solvent is preferable.
一般に、ポリクロロプレン系接着剤組成物は、アルキルフェノール樹脂や酸化マグネシウム（ＭｇＯ）を有機溶剤に溶解させて、２５℃の温度条件下で２０時間静置した反応樹脂溶液に、クロロプレン系重合体、金属酸化物及び老化防止剤をロールで混練したものを溶解させる方法により製造されている。 In general, a polychloroprene-based adhesive composition is prepared by dissolving an alkylphenol resin or magnesium oxide (MgO) in an organic solvent and leaving the reaction resin solution at a temperature of 25 ° C. for 20 hours. It is manufactured by a method in which an oxide and an antioxidant are kneaded with a roll.
これに対して、本実施形態のポリクロロプレン接着剤組成物の製造方法では、クロロプレン系重合体と、金属酸化物と、老化防止剤とを、ロール練りせずに、直接有機溶剤に溶解及び分散させることにより、接着剤組成物を製造することもできる。これにより、前述した反応やロール混練等の準備作業を省略することができる。 In contrast, in the method for producing the polychloroprene adhesive composition of the present embodiment, the chloroprene polymer, the metal oxide, and the anti-aging agent are directly dissolved and dispersed in an organic solvent without kneading in a roll. By making it, an adhesive composition can also be manufactured. Thereby, preparatory work, such as reaction mentioned above and roll kneading | mixing, can be skipped.
このように、本実施形態のポリクロロプレン系接着剤組成物においては、非硫黄変性クロロプレン系重合体に、硫黄変性クロロプレン系重合体を混合しているため、優れた耐熱接着強度を維持しつつ、耐層分離性を向上させることができる。 Thus, in the polychloroprene adhesive composition of the present embodiment, since the sulfur-modified chloroprene polymer is mixed with the non-sulfur-modified chloroprene polymer, while maintaining excellent heat-resistant adhesive strength, The layer separation resistance can be improved.
本実施形態のポリクロロプレン系接着剤組成物は、紙、木材、布、皮革、ジャージ、レザー、ゴム、プラスチック、フォーム、陶器、ガラス、モルタル、セメント系材料、セラミック及び金属等の同種又は異種の材料同士を接着することが可能である。特に、本実施形態のポリクロロプレン系接着剤組成物は、耐熱接着強度に優れるため、木工、家具、建築材料、車両、靴、鞄、ベルト及び各種ラミネーションを接着するための接着剤として好適である。 The polychloroprene adhesive composition of the present embodiment is the same or different kind of paper, wood, cloth, leather, jersey, leather, rubber, plastic, foam, earthenware, glass, mortar, cement-based material, ceramic and metal. It is possible to bond materials together. In particular, since the polychloroprene adhesive composition of the present embodiment is excellent in heat-resistant adhesive strength, it is suitable as an adhesive for bonding woodwork, furniture, building materials, vehicles, shoes, bags, belts and various laminations. .
以下、本発明の実施例及び比較例を挙げて、本発明の効果について具体的に説明する。本実施例においては、以下に示す方法で製造した非硫黄変性クロロプレン系重合体Ａ及び硫黄変性クロロプレン系重合体Ｂを用いて接着剤組成物を作製し、その性能を評価した。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, an adhesive composition was prepared using a non-sulfur-modified chloroprene polymer A and a sulfur-modified chloroprene polymer B produced by the method described below, and the performance was evaluated.
（実施例１）
＜非硫黄変性クロロプレン系重合体Ａの製造＞
水：１２０部、ロジン酸のナトリウム塩（荒川化学工業社製 商品名「ロンジス」）：４．０部、水酸化カリウム：０．５部の乳化剤水溶液に、亜硫酸水素ナトリウム：０．５部を添加した。また、その他の添加剤として、β−ナフタレンスルホン酸ナトリウム塩（花王社製 商品名「デモールＮＬ（登録商標）」）：０．５質量部を仕込んで溶解させた。
Example 1
< Production of non-sulfur modified chloroprene polymer A>
Water: 120 parts, sodium salt of rosin acid (trade name “Longis” manufactured by Arakawa Chemical Industries Ltd.): 4.0 parts, potassium hydroxide: 0.5 parts emulsifier aqueous solution, sodium hydrogen sulfite: 0.5 parts Added. In addition, as other additives, β-naphthalenesulfonic acid sodium salt (trade name “Demol NL (registered trademark)” manufactured by Kao Corporation): 0.5 parts by mass was charged and dissolved.
この溶液を内容積５リットルの反応器に投入し、撹拌しながらクロロプレン単量体：１００質量部及びｎ−ドデシルメルカプタン：０．１質量部を加えた。更に、過硫酸カリウム：０．１質量部を触媒として用いて、窒素ガス雰囲気下で、重合温度を４０℃にして重合し、最終重合率が６５％に達したところでフェノチアジンの乳濁液を加えて重合を停止させた。その後、減圧下で、反応溶液中の未反応単量体を除去した。そして、このラテックスを１０％酢酸水溶液によってｐＨ＝７に調整し、凍結凝固乾燥法により非硫黄変性クロロプレン系重合体Ａのゴムシートを得た。 This solution was put into a reactor having an internal volume of 5 liters, and 100 parts by mass of chloroprene monomer and 0.1 parts by mass of n-dodecyl mercaptan were added while stirring. Furthermore, using 0.1 parts by mass of potassium persulfate as a catalyst, polymerization was carried out at a polymerization temperature of 40 ° C. in a nitrogen gas atmosphere. When the final polymerization rate reached 65%, an emulsion of phenothiazine was added. The polymerization was stopped. Thereafter, unreacted monomers in the reaction solution were removed under reduced pressure. The latex was adjusted to pH = 7 with a 10% aqueous acetic acid solution, and a rubber sheet of non-sulfur-modified chloroprene polymer A was obtained by a freeze coagulation drying method.
＜硫黄変性クロロプレン系重合体Ｂの製造＞
水：１２０部、ロジン酸のナトリウム塩（荒川化学工業社製 商品名「ロンジス」）：４．５部、水酸化カリウム：０．５部の乳化剤水溶液に、亜硫酸水素ナトリウム：０．５部を添加した。また、その他の添加剤として、β−ナフタレンスルホン酸ナトリウム塩（花王社製 商品名「デモールＮＬ（登録商標）」）：０．５質量部を仕込んで溶解させた。
<Production of sulfur-modified chloroprene polymer B>
Water: 120 parts, sodium salt of rosin acid (trade name “Longis” manufactured by Arakawa Chemical Industries): 4.5 parts, potassium hydroxide: 0.5 parts emulsifier aqueous solution, sodium bisulfite: 0.5 parts Added. In addition, as other additives, β-naphthalenesulfonic acid sodium salt (trade name “Demol NL (registered trademark)” manufactured by Kao Corporation): 0.5 parts by mass was charged and dissolved.
この溶液を、内容積５リットルの反応器に投入し、撹拌しながらクロロプレン単量体：１００質量部と硫黄：０．６質量部を加えた。更に、過硫酸カリウム：０．１質量部を触媒として用いて、窒素ガス雰囲気下で、重合温度を４０℃にして重合し、最終重合率が６５％に達したところでフェノチアジンの乳濁液、テトラエチルチウラムジスルフィド：２部の乳濁液及びジブチルジチオカルバミン酸ソーダの水溶液を加えて、重合を停止させた。その後、減圧下で、反応溶液中の未反応単量体を除去した。そして、このラテックスを１０％酢酸水溶液によってｐＨ＝７に調整し、凍結凝固乾燥法により硫黄変性クロロプレン系重合体Ｂのゴムシートを得た。 This solution was put into a reactor having an internal volume of 5 liters, and chloroprene monomer: 100 parts by mass and sulfur: 0.6 parts by mass were added while stirring. Further, potassium persulfate: 0.1 parts by mass as a catalyst was polymerized under a nitrogen gas atmosphere at a polymerization temperature of 40 ° C. When the final polymerization rate reached 65%, an emulsion of phenothiazine, tetraethyl Thiuram disulfide: Two parts of the emulsion and an aqueous solution of sodium dibutyldithiocarbamate were added to stop the polymerization. Thereafter, unreacted monomers in the reaction solution were removed under reduced pressure. The latex was adjusted to pH = 7 with a 10% aqueous acetic acid solution, and a rubber sheet of sulfur-modified chloroprene polymer B was obtained by freeze coagulation drying.
＜ポリクロロプレン系接着剤組成物の製造＞
粘着付与樹脂（フェノール樹脂、「タマノル５２６（登録商標）」）と、酸化マグネシウムを有機溶剤に溶かして、２５℃で２０時間反応させることで樹脂溶液を調製した。そして、この樹脂溶液に、前述した方法で作製した非硫黄変性クロロプレン系重合体Ａからなるゴムシート：９５質量部と、硫黄変性クロロプレン系重合体Ｂからなるゴムシート：５質量部と、老化防止剤として４，４´−チオビス（６−ｔ−ブチル−３−メチルフェノール）（「ノクラックＮ−３００（登録商標）」）：１質量部と、酸化マグネシウム：３質量部と、酸化亜鉛２種（粒径約５００ｎｍ）：１質量部とを直接溶解して、実施例１の接着剤組成物とした。
<Production of polychloroprene adhesive composition>
A resin solution was prepared by dissolving a tackifier resin (phenol resin, “Tamanol 526 (registered trademark))” and magnesium oxide in an organic solvent and reacting at 25 ° C. for 20 hours. And in this resin solution, the rubber sheet consisting of the non-sulfur-modified chloroprene polymer A prepared by the method described above: 95 parts by mass, the rubber sheet consisting of the sulfur-modified chloroprene polymer B: 5 parts by mass, and anti-aging 4,4′-thiobis (6-tert-butyl-3-methylphenol) (“NOCRACK N-300 (registered trademark)”): 1 part by mass, magnesium oxide: 3 parts by mass, and two types of zinc oxide (Particle size: about 500 nm): 1 part by mass was directly dissolved to obtain an adhesive composition of Example 1.
（実施例２〜７）
非硫黄変性クロロプレン系重合体Ａからなるゴムシートと、硫黄変性クロロプレン系重合体Ｂからなるゴムシートの配合比を変えて、それ以外は実施例１と同様の条件にして、実施例２、３の接着剤組成物を作製した。また、連鎖移動剤を使用せずに重合を行った非硫黄変性クロロプレン系重合体と、硫黄添加量を変えて重合した硫黄変性クロロプレン系重合体を使用した以外は、前述した実施例１と同様にして、実施例４の接着剤組成物を作製した。
(Examples 2 to 7)
Examples 2 and 3 were carried out under the same conditions as in Example 1, except that the compounding ratio of the rubber sheet made of non-sulfur-modified chloroprene polymer A and the rubber sheet made of sulfur-modified chloroprene polymer B was changed. An adhesive composition was prepared. Further, the same as Example 1 described above except that a non-sulfur modified chloroprene polymer polymerized without using a chain transfer agent and a sulfur modified chloroprene polymer polymerized by changing the amount of sulfur added were used. Thus, an adhesive composition of Example 4 was produced.
一方、酸化亜鉛２種の代わりに、酸化亜鉛（「ＭＥＴＡＺ−１０２（登録商標），粒径約１００ｎｍ」を使用して、それ以外は前述した実施例１と同様にして、実施例５の接着剤組成物を作製した。また、硫黄変性クロロプレン系重合体の配合量をクロロプレン系重合体全体の５０質量％とし、それ以外は、実施例１と同様にして、実施例６の接着剤組成物を作製した。更に、硫黄変性クロロプレン系重合体Ｂを、クロロプレン：９０質量部及びジクロロブタジエン：１０質量部の共重合体とした以外は、実施例１と同様にして、実施例７の接着剤組成物を作製した。 On the other hand, in place of the two types of zinc oxide, zinc oxide (“METAZ-102 (registered trademark), particle size of about 100 nm”) was used, and other than that, the adhesion of Example 5 was performed in the same manner as in Example 1 described above. An adhesive composition of Example 6 was prepared in the same manner as in Example 1 except that the amount of the sulfur-modified chloroprene polymer was 50% by mass of the entire chloroprene polymer. Furthermore, the adhesive of Example 7 was the same as Example 1 except that the sulfur-modified chloroprene polymer B was a copolymer of 90 parts by mass of chloroprene and 10 parts by mass of dichlorobutadiene. A composition was prepared.
（比較例１）
硫黄変性クロロプレン重合体Ｂを配合していない以外は、前述した実施例１と同様にして、比較例１の接着剤組成物を作製した。
(Comparative Example 1)
An adhesive composition of Comparative Example 1 was produced in the same manner as in Example 1 except that the sulfur-modified chloroprene polymer B was not blended.
実施例及び比較例の各接着剤組成物の配合を、下記表１に示す。また、このようにして得られた実施例及び比較例の各接着剤組成物について、以下に示す方法で、溶液粘度、接着剥離強度、耐熱接着剥離強度及びスプレー塗工作業性を評価した。 Table 1 below shows the composition of each adhesive composition of Examples and Comparative Examples. Moreover, about the adhesive composition of the Example and comparative example which were obtained in this way, solution viscosity, adhesive peeling strength, heat-resistant adhesive peeling strength, and spray coating workability | operativity were evaluated by the method shown below.
[溶液粘度]
実施例及び比較例の各接着剤組成物の溶液粘度は、ブルックスフィールド粘度計を用いて、温度２０℃、３０ｒｐｍの条件で測定した。
[Solution viscosity]
The solution viscosity of each adhesive composition in Examples and Comparative Examples was measured using a Brooksfield viscometer at a temperature of 20 ° C. and 30 rpm.
＜接着剥離強度＞
帆布（２５ｍｍ×１５０ｍｍ）２枚それぞれに、実施例及び比較例の各接着剤組成物を３０００ｇ／ｃｍ２塗布した。その後、オープンタイムを３０分として、ハンドローラーで５往復した。そして、セットタイム３時間後の初期強度と、１０日後の常態強度を５０ｍｍ／ｍｉｎの引張強度で測定した。
<Adhesive peel strength>
3000 g / cm 2 of each of the adhesive compositions of Examples and Comparative Examples was applied to two canvases (25 mm × 150 mm). Thereafter, the open time was set to 30 minutes, and the hand roller made 5 round trips. Then, the initial strength after 3 hours of set time and the normal strength after 10 days were measured with a tensile strength of 50 mm / min.
＜耐熱接着剥離強＞
帆布（２５ｍｍ×１５０ｍｍ）２枚それぞれに、実施例及び比較例の各接着剤組成物を３０００ｇ／ｃｍ２塗布した。その後、オープンタイムを３０分として、ハンドローラーで５往復した。そして、セットタイム１０日後の被着体を、８０℃の恒温槽付きの引張試験機で５０ｍｍ／ｍｉｎの条件で剥離強度を測定した。
<Heat-resistant adhesive peel strength>
3000 g / cm 2 of each of the adhesive compositions of Examples and Comparative Examples was applied to two canvases (25 mm × 150 mm). Thereafter, the open time was set to 30 minutes, and the hand roller made 5 round trips. Then, the peel strength of the adherend after 10 days of set time was measured under the condition of 50 mm / min with a tensile tester equipped with a thermostat at 80 ° C.
＜軟化点試験＞
帆布（２５ｍｍ×１５０ｍｍ）２枚それぞれに、実施例及び比較例の各接着剤組成物を３０００ｇ／ｍ２塗布した。その後、オープンタイムを３０分として、ハンドローラーで５往復した。そして、セットタイム１０日後の試験体を、５００ｇの重りを吊り下げた状態で、試験装置内にセットし、試験装置内を３８℃雰囲気下で１５分間保持後、５分間に２℃の割合で昇温し、重りが落下する温度を測定した。
<Softening point test>
Each of the two canvas fabrics (25 mm × 150 mm) was coated with 3000 g / m 2 of each of the adhesive compositions of Examples and Comparative Examples. Thereafter, the open time was set to 30 minutes, and the hand roller made 5 round trips. Then, the test body 10 days after the set time is set in the test apparatus with a weight of 500 g suspended, and the test apparatus is held in a 38 ° C. atmosphere for 15 minutes, and then at a rate of 2 ° C. for 5 minutes. The temperature was raised and the temperature at which the weight dropped was measured.
＜接着剤の耐層分離安定性＞
実施例及び比較例の各接着剤組成物をガラス瓶に入れ、５０℃で４週間放置後の溶液状態を観察した。そして、均一であったものを○、層分離が顕著な状態のものを×とした。
<Stability of layer separation resistance of adhesive>
Each adhesive composition of the example and the comparative example was put in a glass bottle, and the solution state after standing at 50 ° C. for 4 weeks was observed. And the thing which was in a state with remarkable layer separation was set as (circle) and the thing which was uniform.
＜接着剤の貯蔵安定性＞
実施例及び比較例の各接着剤組成物をガラス瓶に入れた直後と、５０℃で４週間後の溶液粘度測定を、ブルックフィールド型粘度計により測定した。
<Storage stability of adhesive>
Immediately after putting each adhesive composition of an Example and a comparative example in a glass bottle, and the solution viscosity measurement after 4 weeks at 50 degreeC were measured with the Brookfield type | mold viscosity meter.
以上の結果を、下記表２にまとめて示す。 The above results are summarized in Table 2 below.
上記表２に示すように、硫黄変性クロロプレン系重合体を配合していない比較例１の接着剤組成物は、耐層分離性に劣り、耐熱接着強度も低いものであった。これに対して、本発明の範囲内で作製した実施例１〜７の接着剤樹脂組成物は、耐層分離性に優れ、耐熱接着強度も高かった。これにより、本発明によれば、耐熱接着力及び耐層分離性の両方が優れたポリクロロプレン系接着剤組成物を実現できることが確認された。 As shown in Table 2 above, the adhesive composition of Comparative Example 1 in which no sulfur-modified chloroprene polymer was blended was inferior in layer separation resistance and low in heat resistant adhesive strength. On the other hand, the adhesive resin compositions of Examples 1 to 7 produced within the scope of the present invention were excellent in layer separation resistance and high in heat-resistant adhesive strength. Thereby, according to this invention, it was confirmed that the polychloroprene-type adhesive composition excellent in both the heat-resistant adhesive force and the delamination-proof property is realizable.
本発明に係るポリクロロプレン系接着剤組成物は、紙、木質材、布類、皮革類、ジャージ、合成レザー類、ゴム類、プラスチック類、陶器、セラミックス、ガラス、モルタル、セメント、金属類等の幅広い材料の接着剤等として好適に用いることができる。 The polychloroprene adhesive composition according to the present invention includes paper, wood, cloth, leather, jersey, synthetic leather, rubber, plastics, ceramics, ceramics, glass, mortar, cement, metals, etc. It can be suitably used as an adhesive for a wide range of materials.
Claims (13)
硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して得た硫黄変性クロロプレン系重合体と、
有機溶剤と、を含有し、
前記非硫黄変性クロロプレン系重合体及び前記硫黄変性クロロプレン系重合体が、前記有機溶剤中に溶解しているポリクロロプレン系接着剤組成物。 A non-sulfur modified chloroprene polymer obtained by polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene;
A sulfur-modified chloroprene polymer obtained by polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene in the presence of sulfur;
An organic solvent,
The polychloroprene adhesive composition in which the non-sulfur-modified chloroprene polymer and the sulfur-modified chloroprene polymer are dissolved in the organic solvent.
硫黄存在下で、クロロプレンを単独で重合するか又はクロロプレンを含む２種以上の単量体を共重合して硫黄変性クロロプレン系重合体を得る工程と、
有機溶剤に、前記非硫黄変性クロロプレン系重合体及び前記硫黄変性クロロプレン系重合体を溶解する工程と、
を有するポリクロロプレン系接着剤組成物の製造方法。 A step of polymerizing chloroprene alone or copolymerizing two or more monomers containing chloroprene to obtain a non-sulfur-modified chloroprene polymer;
A step of polymerizing chloroprene alone in the presence of sulfur or copolymerizing two or more monomers containing chloroprene to obtain a sulfur-modified chloroprene polymer;
Dissolving the non-sulfur modified chloroprene polymer and the sulfur modified chloroprene polymer in an organic solvent;
The manufacturing method of the polychloroprene-type adhesive composition which has this.
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