JP2013133466A - Adhesive - Google Patents
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- JP2013133466A JP2013133466A JP2011286942A JP2011286942A JP2013133466A JP 2013133466 A JP2013133466 A JP 2013133466A JP 2011286942 A JP2011286942 A JP 2011286942A JP 2011286942 A JP2011286942 A JP 2011286942A JP 2013133466 A JP2013133466 A JP 2013133466A
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本発明は、自己選択的粘着性を有する粘着剤、及び該粘着剤を含有するアルコール溶液に関する。 The present invention relates to an adhesive having self-selective adhesiveness, and an alcohol solution containing the adhesive.
粘着剤同士は強く粘着するが、他のものには粘着力が低い粘着剤、すなわち自己選択性を有する粘着剤（以下「自己選択的粘着剤」ともいう）は野菜や生花の結束用テープや毛髪セット剤等に使用されている。自己選択的粘着剤は、例えば毛髪セット剤に応用した場合、粘着剤同士は高い粘着力を示す（以下「自己選択的粘着性」ともいう）ため、高いセット力を有するが、指等、他者との間での粘着力は低いため、べたつき等が少ないという利点を有する。かかる粘着剤としては、天然ゴム、合成ゴムなどに粘着付与剤、軟化剤を配合してなるものが知られている（例えば、特許文献１及び２）。しかしながら、このようなゴム系粘着剤は、耐候性、耐熱性及び保存安定性が十分に満足できるものではない。
そこで、耐候性、耐熱性及び保存安定性を改善する目的で、汎用アクリル系ポリマーをベースとして開発された粘着剤が知られている（例えば、特許文献３及び４）。
Adhesives strongly adhere to each other, but others have low adhesive strength, that is, self-selective adhesives (hereinafter also referred to as “self-selective adhesives”) Used in hair setting agents. For example, when the self-selective pressure-sensitive adhesive is applied to a hair setting agent, the pressure-sensitive adhesives exhibit high adhesive strength (hereinafter also referred to as “self-selective adhesiveness”). Since the adhesive strength with a person is low, there is an advantage that there is little stickiness or the like. As such a pressure-sensitive adhesive, a material obtained by blending a natural rubber, a synthetic rubber or the like with a tackifier and a softener is known (for example, Patent Documents 1 and 2). However, such a rubber-based pressure-sensitive adhesive is not sufficiently satisfactory in weather resistance, heat resistance and storage stability.
Thus, pressure-sensitive adhesives developed based on general-purpose acrylic polymers for the purpose of improving weather resistance, heat resistance and storage stability are known (for example, Patent Documents 3 and 4).
しかしながら、特許文献３及び４に開示されたアクリル系粘着剤は、溶解できる溶媒が限られているため、配合や加工の際の自由度が低く、特に水や低級アルコール等への溶解性が低いことから、香粧品関連製品への応用が困難であった。また、上記アクリル系粘着剤においては、粘着剤のマトリクスとなる成分として自己選択的粘着性が低い粘着付与成分を添加するため、べたつきが排除できないという問題があった。 However, since the acrylic pressure-sensitive adhesives disclosed in Patent Documents 3 and 4 have limited solvents that can be dissolved, the degree of freedom during blending and processing is low, and in particular, the solubility in water and lower alcohols is low. Therefore, application to cosmetics-related products was difficult. Moreover, in the said acrylic adhesive, since the tackifying component with low self-selective adhesiveness is added as a component used as an adhesive matrix, there existed a problem that stickiness cannot be excluded.
本発明の課題は、低級アルコールに溶解することができ、かつ粘着付与剤を必要とせず、べたつきを低減したアクリル系自己選択的粘着剤、及び該粘着剤を含有するアルコール溶液を提供することにある。 An object of the present invention is to provide an acrylic self-selective pressure-sensitive adhesive that can be dissolved in a lower alcohol, does not require a tackifier, and has reduced stickiness, and an alcohol solution containing the pressure-sensitive adhesive. is there.
本発明者らは、特定の構造を有するアクリル系ポリマーからなる粘着剤が上記要求を満たす粘着剤となることを見出した。
すなわち、本発明は、下記［１］及び［２］を提供するものである。
［１］下記一般式（１）で表される構成単位の含有量が５０〜１００質量％であり、重量平均分子量が１５〜４０万であって、かつ重量平均分子量１万以下のポリマーの含有量が３質量％以下であるポリマーからなる粘着剤。
The present inventors have found that a pressure-sensitive adhesive made of an acrylic polymer having a specific structure is a pressure-sensitive adhesive that satisfies the above requirements.
That is, the present invention provides the following [1] and [2].
[1] Content of a polymer having a structural unit represented by the following general formula (1) of 50 to 100% by mass, a weight average molecular weight of 150 to 400,000, and a weight average molecular weight of 10,000 or less A pressure-sensitive adhesive comprising a polymer having an amount of 3% by mass or less.
〔式中、Ｒは水素原子、アルカリ金属原子又は炭素数１〜１２の炭化水素基であって、ポリマー中複数のＲは互いに同一又は異なって、ポリマー分子中におけるＲの炭素数の数平均値は１〜３である。〕
［２］前記［１］の粘着剤を炭素数１〜４のアルコールから選ばれる１種以上の溶媒に溶解したアルコール溶液。
[In the formula, R is a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R in the polymer are the same or different from each other, and the number average value of the carbon number of R in the polymer molecule] Is 1-3. ]
[2] An alcohol solution obtained by dissolving the pressure-sensitive adhesive of [1] in one or more solvents selected from alcohols having 1 to 4 carbon atoms.
本発明により、低級アルコールに溶解することができ、かつべたつきを低減したアクリル系自己選択的粘着剤、及び該粘着剤を含有するアルコール溶液を提供することができる。 According to the present invention, an acrylic self-selective pressure-sensitive adhesive that can be dissolved in a lower alcohol and has reduced stickiness, and an alcohol solution containing the pressure-sensitive adhesive can be provided.
［粘着剤］
本発明の粘着剤は、下記一般式（１）で表される構成単位の含有量が５０〜１００質量％であり、重量平均分子量が１５〜４０万であって、かつ重量平均分子量１万以下のポリマーの含有量が３質量％以下であるポリマー（以下、「本発明のポリマー」ともいう）からなる。
[Adhesive]
In the pressure-sensitive adhesive of the present invention, the content of the structural unit represented by the following general formula (1) is 50 to 100% by mass, the weight average molecular weight is 150 to 400,000, and the weight average molecular weight is 10,000 or less. The polymer content is 3% by mass or less (hereinafter also referred to as “the polymer of the present invention”).
＜本発明のポリマー＞
下記一般式（１）において、Ｒは水素原子、アルカリ金属原子又は炭素数１〜１２の炭化水素基であって、ポリマー中複数のＲは互いに同一又は異なって、ポリマー分子中におけるＲの炭素数の数平均値は１〜３である。なお、ポリマー分子中におけるＲの炭素数の数平均値は、本発明のポリマーのＲが水素原子、又はアルカリ金属原子である構成単位を含む場合には、水素原子又はアルカリ金属原子であるＲの炭素数を０と換算して算出するものとする。
<Polymer of the present invention>
In the following general formula (1), R is a hydrogen atom, an alkali metal atom, or a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R's in the polymer are the same or different from each other, and the carbon number of R in the polymer molecule The number average value of is 1-3. In addition, the number average value of the carbon number of R in the polymer molecule is the value of R of a hydrogen atom or an alkali metal atom when R of the polymer of the present invention includes a structural unit that is a hydrogen atom or an alkali metal atom. The number of carbon atoms is calculated by converting to zero.
本発明の粘着剤のべたつきを小さくするためには、常温における本発明のポリマーの弾性が適度に高いことが必要であり、この観点から、ポリマー分子中におけるＲの炭素数の数平均値は１．５〜２．５であることが好ましく、１．７〜２．３であることがより好ましく、１．８〜２．２であることが更に好ましい。
Ｒの具体例としては、水素原子、ナトリウム原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチル‐ヘキシル基、及びラウリル基等が挙げられる。
前記低級アルコールへの溶解性及びべたつき抑制の観点から、Ｒは、水素原子、アルカリ金属原子、及びメチル基、エチル基、ｎ−プロピル基又はイソプロピル基の炭素数１〜３のアルキル基であることが好ましく、メチル基、エチル基、ｎ−プロピル基又はイソプロピル基であることがより好ましく、エチル基であることが更に好ましい。
自己選択的粘着性発現の観点から、本発明のポリマーは、前記一般式（１）で表される構成単位を５０〜１００質量％含有するものであり、８０〜１００質量％含有することが好ましく、９０〜１００質量％含有することがより好ましく、９５〜１００質量％含有することが更に好ましい。
In order to reduce the stickiness of the pressure-sensitive adhesive of the present invention, it is necessary that the elasticity of the polymer of the present invention is moderately high at room temperature. From this viewpoint, the number average value of the carbon number of R in the polymer molecule is 1 It is preferably 0.5 to 2.5, more preferably 1.7 to 2.3, and still more preferably 1.8 to 2.2.
Specific examples of R include hydrogen atom, sodium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-hexyl group, Examples include n-octyl group, 2-ethyl-hexyl group, and lauryl group.
From the viewpoint of solubility in the lower alcohol and suppression of stickiness, R is a hydrogen atom, an alkali metal atom, and an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Are preferred, more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and even more preferably an ethyl group.
From the viewpoint of self-selective adhesive expression, the polymer of the present invention contains 50 to 100% by mass of the structural unit represented by the general formula (1), and preferably contains 80 to 100% by mass. 90 to 100% by mass, more preferably 95 to 100% by mass.
ポリマー分子中、前記一般式（１）で表される構成単位以外の部位の構造については、特に限定はない。例えば、本発明のポリマー製造の際に、重合開始剤や連鎖移動剤を用いる場合には、本発明のポリマーには、重合開始剤や連鎖移動剤に由来する基が含まれることがある。また、前記一般式（１）で表される構成単位に対応するモノマー（以下、「モノマー（１）」ともいう）と共重合可能なモノマー由来の構造を、本発明の効果を損なわない範囲で有していてよい。
ここで、一般式（１）で表される構成単位に対応するモノマーとは、該モノマーを重合させることで、得られたポリマー中に前記一般式（１）で表される構成単位を生じさせるモノマーをいい、具体例については後述する。
There is no particular limitation on the structure of the polymer molecule other than the structural unit represented by the general formula (1). For example, when a polymerization initiator or a chain transfer agent is used in the production of the polymer of the present invention, the polymer of the present invention may contain a group derived from the polymerization initiator or the chain transfer agent. In addition, a structure derived from a monomer copolymerizable with a monomer corresponding to the structural unit represented by the general formula (1) (hereinafter, also referred to as “monomer (1)”) is within a range not impairing the effects of the present invention. You may have.
Here, the monomer corresponding to the structural unit represented by the general formula (1) means that the structural unit represented by the general formula (1) is generated in the obtained polymer by polymerizing the monomer. A monomer is mentioned and a specific example will be described later.
本発明のポリマーの重量平均分子量は、本発明の粘着剤のべたつきを抑制する観点から１５万以上であり、本発明の粘着剤同士においては高い粘着力を発現する観点から４０万以下である。すなわち、自己選択的粘着性を有する観点から、本発明のポリマーの重量平均分子量は１５〜４０万であり、１５〜３０万が好ましく、１５〜２５万がより好ましい。
同様に、本発明のポリマー中において、重量平均分子量１万以下のポリマーの含有量は、低分子量成分によるべたつきを抑制する観点から、ポリマー全体の３質量％以下であり、２質量％以下であることが好ましく、１質量％以下であることがより好ましい。
このように、本発明のポリマー中の低分子量成分の含有量は低減することが好ましいが、低分子量成分を全く含有しないポリマーを得ることは困難である。この観点から、本発明のポリマー中において、重量平均分子量１万以下のポリマーの含有量は０．００１質量％以上であることが好ましい。
The weight average molecular weight of the polymer of the present invention is 150,000 or more from the viewpoint of suppressing the stickiness of the pressure-sensitive adhesive of the present invention, and is 400,000 or less from the viewpoint of expressing high adhesive strength between the pressure-sensitive adhesives of the present invention. That is, from the viewpoint of having self-selective tackiness, the polymer of the present invention has a weight average molecular weight of 150 to 400,000, preferably 15 to 300,000, and more preferably 15 to 250,000.
Similarly, in the polymer of the present invention, the content of the polymer having a weight average molecular weight of 10,000 or less is 3% by mass or less and 2% by mass or less of the whole polymer from the viewpoint of suppressing stickiness due to low molecular weight components. It is preferably 1% by mass or less.
Thus, although it is preferable to reduce the content of the low molecular weight component in the polymer of the present invention, it is difficult to obtain a polymer that does not contain any low molecular weight component. From this viewpoint, the content of the polymer having a weight average molecular weight of 10,000 or less in the polymer of the present invention is preferably 0.001% by mass or more.
本発明のポリマーの形状は、直鎖構造が好ましいが分岐構造を有していてもよい。溶解性の観点から、架橋構造は有さない方が好ましい。 The polymer of the present invention preferably has a linear structure, but may have a branched structure. From the viewpoint of solubility, it is preferable not to have a crosslinked structure.
＜本発明のポリマーの製造方法＞
本発明のポリマーの製造方法に特に限定は無いが、ポリマーの重量平均分子量を前述した範囲に制御する観点から、モノマー（１）を含む原料モノマー溶液中で溶液重合を行って製造する方法が好ましい。
<Method for producing the polymer of the present invention>
The method for producing the polymer of the present invention is not particularly limited, but from the viewpoint of controlling the weight average molecular weight of the polymer within the above-mentioned range, a method of producing by polymerizing in a raw material monomer solution containing the monomer (1) is preferable. .
（原料モノマー）
本発明のポリマーの原料に用いるモノマー（１）は、下記一般式（２）で表される化合物である。
(Raw material monomer)
The monomer (1) used for the raw material of the polymer of the present invention is a compound represented by the following general formula (2).
前記一般式（２）において、Ｒは水素原子又はアルカリ金属原子又は炭素数１〜１２の炭化水素基であって、具体例及び好ましいものは前記一般式（１）において例示したものと同様である。
モノマー（１）の具体例としては、アクリル酸及びそのアルカリ金属塩の他、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、ｓｅｃ−ブチルアクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、ｎ−ヘキシルアクリレート、ｎ−オクチルアクリレート、２−エチルヘキシルアクリレート、及びラウリルアクリレート等の、炭素数１〜１２の炭化水素基を有するアクリル酸エステルが挙げられる。ポリマー分子中における前記一般式（１）のＲの炭素数の数平均値が１〜３となる範囲で、上記モノマー（１）を単独で、又は２種以上を組み合わせて用いることができる。
モノマー（１）としては、本発明の粘着剤の溶解性及びべたつき抑制の観点から、アクリル酸及びそのアルカリ金属塩の他、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート等の炭素数１〜３の炭化水素基を有するアクリル酸エステルが好ましく、エチルアクリレートがより好ましい。
In the general formula (2), R represents a hydrogen atom, an alkali metal atom, or a hydrocarbon group having 1 to 12 carbon atoms, and specific examples and preferable examples are the same as those exemplified in the general formula (1). .
Specific examples of the monomer (1) include acrylic acid and alkali metal salts thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, t-butyl. Examples thereof include acrylic esters having a hydrocarbon group having 1 to 12 carbon atoms, such as acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. The said monomer (1) can be used individually or in combination of 2 or more types in the range from which the number average value of the carbon number of R of the said General formula (1) in a polymer molecule becomes 1-3.
As the monomer (1), from the viewpoint of the solubility and stickiness suppression of the pressure-sensitive adhesive of the present invention, in addition to acrylic acid and its alkali metal salt, carbon number 1 such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, etc. Acrylic acid ester having ˜3 hydrocarbon groups is preferred, and ethyl acrylate is more preferred.
原料モノマーとしては、モノマー（１）以外の他のモノマー（以下、「その他のモノマー」ともいう。）を本発明の効果を妨げない範囲で用いることもできる。その他のモノマーとしは下記一般式（３）で表される化合物である。 As the raw material monomer, other monomers (hereinafter also referred to as “other monomers”) other than the monomer (1) can be used as long as the effects of the present invention are not hindered. Other monomers are compounds represented by the following general formula (3).
前記一般式（３）において、Ｒ1は水素原子又はメチル基であって、Ｘは、ＣＯ2Ｒ2、ＣＯＮＲ3Ｒ4又はＯＣＯＲ5である。ＸにおけるＲ2は水素原子、アルカリ金属原子、炭素数１〜３０の炭化水素基又は炭素数１〜３０の含酸素炭化水素基であって、Ｒ3〜Ｒ5はそれぞれ水素原子又は炭素数１〜３０の炭化水素基である。ただし、その他のモノマーはモノマー（１）を含まないため、Ｒ1が水素原子のときＲ2は炭素数１３〜３０の炭化水素基又は炭素数１〜３０の含酸素炭化水素基である。
その他のモノマーの具体例としては、炭素数１３〜３０の炭化水素基又は炭素数１〜３０の含酸素炭化水素基を有するアクリル酸エステル（前記モノマー（１）を除く）、メタクリル酸及びそのアルカリ金属塩、炭素数１〜３０の炭化水素基又は炭素数１〜３０の含酸素炭化水素基を有するメタクリル酸エステル、アクリルアミド、炭素数１〜１５の炭化水素基を有するアクリルアミド、メタクリルアミド、炭素数１〜１５の炭化水素基を有するメタクリルアミド、並びに炭素数１〜３０の脂肪酸ビニル等の、モノマー（１）と共重合可能な不飽和結合を有するモノマーが挙げられる。その他のモノマーは、単独で又は２種以上を組み合わせて用いることができる。
In the general formula (3), R 1 is a hydrogen atom or a methyl group, and X is CO 2 R 2 , CONR 3 R 4 or OCOR 5 . R 2 in X is a hydrogen atom, an alkali metal atom, a hydrocarbon group having 1 to 30 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 30 carbon atoms, and R 3 to R 5 are each a hydrogen atom or 1 carbon atom. ~ 30 hydrocarbon groups. However, since the other monomer does not contain the monomer (1), when R 1 is a hydrogen atom, R 2 is a hydrocarbon group having 13 to 30 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 30 carbon atoms.
Specific examples of other monomers include acrylic acid esters having a hydrocarbon group having 13 to 30 carbon atoms or an oxygen-containing hydrocarbon group having 1 to 30 carbon atoms (excluding the monomer (1)), methacrylic acid, and alkalis thereof. Metal salt, methacrylic acid ester having 1 to 30 carbon atoms or oxygen-containing hydrocarbon group having 1 to 30 carbon atoms, acrylamide, acrylamide having 1 to 15 carbon atoms, methacrylamide, carbon number Examples thereof include a monomer having an unsaturated bond copolymerizable with the monomer (1), such as methacrylamide having 1 to 15 hydrocarbon groups and fatty acid vinyl having 1 to 30 carbon atoms. Other monomers can be used alone or in combination of two or more.
原料モノマーとして、モノマー（１）とその他のモノマーで挙げたモノマーの混合物を用いる場合には、粘着剤のべたつきを小さくする観点から、モノマーあたりの炭化水素基の炭素数の平均値が、前述したポリマー分子中におけるＲの炭素数の数平均値の範囲に入るように、モノマーの種類、及び混合組成を選択することが好ましい。
その他のモノマーの炭化水素基の炭素数とは、具体的には一般式（３）において、Ｒ1＋Ｒ2又はＲ1＋Ｒ3＋Ｒ4又はＲ1＋Ｒ5で表される炭化水素基の合計の炭素数である。
In the case of using a mixture of monomers (1) and other monomers mentioned as the raw material monomer, the average value of the number of carbon atoms of the hydrocarbon group per monomer is described above from the viewpoint of reducing the stickiness of the pressure-sensitive adhesive. It is preferable to select the type of monomer and the composition of the mixture so as to fall within the range of the number average value of the carbon number of R in the polymer molecule.
Specifically, the carbon number of the hydrocarbon group of the other monomer is the total number of hydrocarbon groups represented by R 1 + R 2 or R 1 + R 3 + R 4 or R 1 + R 5 in the general formula (3). Carbon number.
原料モノマー中のモノマー（１）の含有量は、本発明のポリマーの自己選択的粘着性発現の観点から、５０〜１００質量％が好ましく、８０〜１００質量％がより好ましく、９０〜１００質量％が更に好ましく、９５〜１００質量％が最も好ましい。 The content of the monomer (1) in the raw material monomer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass from the viewpoint of self-selective adhesive expression of the polymer of the present invention. Is more preferable, and 95-100 mass% is the most preferable.
（開始剤）
本発明のポリマー製造時には、必要に応じて開始剤を用いることができる。開始剤としては、一般に用いられているラジカル重合性開始剤、例えば、過硫酸アンモニウム、過硫酸ナトリウムなどの過硫酸塩、２,２’−アゾビスイソブチロニトリル、２,２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系開始剤、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイドなどの過酸化物系開始剤などを用いることができる。このうち、分解温度や取扱いの容易さの観点から２,２’−アゾビス（２，４−ジメチルバレロニトリル）が好ましい。
開始剤の使用量は、本発明のポリマーの重量平均分子量を、前記の好ましい範囲に制御する観点から、原料モノマーの全量１００質量部に対して０．０１〜５質量部が好ましく、０．０５〜１質量部がより好ましい。
(Initiator)
In the production of the polymer of the present invention, an initiator can be used as necessary. As the initiator, generally used radical polymerizable initiators such as persulfates such as ammonium persulfate and sodium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 Azo initiator such as t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, and the like. Of these, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of decomposition temperature and ease of handling.
The amount of the initiator used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of raw material monomers from the viewpoint of controlling the weight average molecular weight of the polymer of the present invention within the above preferred range. -1 mass part is more preferable.
（溶剤）
本発明のポリマー製造時には、ポリマーの重量平均分子量を制御する観点から、溶剤を用いることが好ましい。溶剤の種類に特に限定はなく、前記原料モノマーと生成ポリマーを溶解可能であればよい。具体的にはアセトン、２−ブタノン等の炭素数３〜５のケトン；メタノール、エタノール、イソプロパノール等の炭素数１〜３のアルコール；水等が挙げられ、多種のモノマー溶解性を有し、後述する重合温度範囲内に沸点を有するため反応制御しやすい、アセトン及び２−ブタノンが好ましく、アセトンがより好ましい。
溶剤の使用量にも特に限定はないが、一般に原料モノマーに対して０．１〜２０質量倍であり、先述の分子量制御の観点から、０．３〜１０質量倍が好ましい。
(solvent)
In producing the polymer of the present invention, it is preferable to use a solvent from the viewpoint of controlling the weight average molecular weight of the polymer. There are no particular limitations on the type of solvent, as long as the raw material monomer and the generated polymer can be dissolved. Specific examples include ketones having 3 to 5 carbon atoms such as acetone and 2-butanone; alcohols having 1 to 3 carbon atoms such as methanol, ethanol and isopropanol; water and the like. Acetone and 2-butanone, which have a boiling point within the polymerization temperature range and are easy to control the reaction, are preferred, and acetone is more preferred.
The amount of the solvent used is not particularly limited, but is generally 0.1 to 20 times by mass with respect to the raw material monomer, and is preferably 0.3 to 10 times by mass from the viewpoint of controlling the molecular weight described above.
（重合条件）
重合温度は、使用する開始剤の種類等によって異なるため一概には決められないが、重合速度の観点から２０℃以上が好ましく、設備負荷低減の観点から１００℃以下が好ましい。上記観点から、４０〜８０℃がより好ましい。重合時間は重合温度や開始剤量等によって異なるため一概には決められないが、通常、１〜１２時間であり、２〜８時間が好ましい。
(Polymerization conditions)
The polymerization temperature varies depending on the type of initiator used and the like, and thus cannot be determined unconditionally, but is preferably 20 ° C. or higher from the viewpoint of polymerization rate, and preferably 100 ° C. or lower from the viewpoint of reducing equipment load. From the said viewpoint, 40-80 degreeC is more preferable. The polymerization time varies depending on the polymerization temperature, the amount of initiator, etc., and thus cannot be determined unconditionally, but is usually 1 to 12 hours, and preferably 2 to 8 hours.
（精製処理）
本発明のポリマー製造時には、重合後、必要に応じて、溶剤の留去、残存モノマーの減圧除去、ゲル濾過クロマトグラフィ、及び再沈殿等、公知の方法によって精製処理を行うことができる。
(Purification treatment)
In the production of the polymer of the present invention, after the polymerization, if necessary, purification treatment can be performed by a known method such as evaporation of the solvent, removal of the residual monomer under reduced pressure, gel filtration chromatography, and reprecipitation.
本発明の粘着剤には必要に応じて、本発明の粘着剤の自己選択的粘着性を消失させない範囲で、無機又は有機の粉体、充填材、可塑剤等を添加することができる。 If necessary, inorganic or organic powders, fillers, plasticizers and the like can be added to the pressure-sensitive adhesive of the present invention as long as the self-selective tackiness of the pressure-sensitive adhesive of the present invention is not lost.
＜アルコール溶液＞
本発明の粘着剤は、炭素数１〜４のアルコールから選ばれる１種以上の溶媒に対して容易に溶解し、本発明の粘着剤を含有するアルコール溶液（以下「本発明のアルコール溶液」ともいう）を形成しうるため、物品表面への薄い粘着剤塗膜形成が容易であり、特に、ハロゲン系溶剤や芳香族系溶剤の使用が困難な香粧品分野の各種製品への応用に有利である。
本発明のアルコール溶液に用いられる炭素数１〜４のアルコールの具体例としては、メタノール、エタノール、イソプロパノール、ブタノール等が例示され、揮発性の高さ、香粧品分野での配合の自由度の観点から、エタノールが好ましい。炭素数１〜４のアルコールは、単独で用いてもよいし、２種以上を混合して用いてもよい。
本発明の粘着剤のアルコールに対する溶解性の観点から、本発明の粘着剤の濃度が０．０１質量％となるように調製したアルコール溶液における、波長６６０ｎｍの光透過率が９０％以上であることが好ましい。この透過率が高いほどアルコールに対する溶解性が高いことを示すことから、この透過率が９３％以上であることがより好ましく、９５％以上であることが更に好ましい。
<Alcohol solution>
The pressure-sensitive adhesive of the present invention is easily dissolved in one or more solvents selected from alcohols having 1 to 4 carbon atoms, and contains an alcohol solution containing the pressure-sensitive adhesive of the present invention (hereinafter referred to as “the alcohol solution of the present invention”). It is easy to form a thin adhesive film on the surface of an article, and is particularly advantageous for application to various products in the cosmetics field where it is difficult to use halogen solvents or aromatic solvents. is there.
Specific examples of the alcohol having 1 to 4 carbon atoms used in the alcohol solution of the present invention include methanol, ethanol, isopropanol, butanol and the like, and have a high volatility and a viewpoint of the degree of freedom of blending in the cosmetics field. Therefore, ethanol is preferable. A C1-C4 alcohol may be used independently and may be used in mixture of 2 or more types.
From the viewpoint of the solubility of the pressure-sensitive adhesive of the present invention in alcohol, the light transmittance at a wavelength of 660 nm in the alcohol solution prepared so that the concentration of the pressure-sensitive adhesive of the present invention is 0.01% by mass is 90% or more. Is preferred. Since this higher transmittance indicates higher solubility in alcohol, the transmittance is more preferably 93% or more, and still more preferably 95% or more.
本発明のアルコール溶液中の該粘着剤の含有量は、粘着力及び塗膜形成操作の容易性の観点から０．００１〜２０質量％が好ましく、０．００２〜５質量％がより好ましく、０．００５〜２質量％が更に好ましく、０．０１〜１質量％がより更に好ましい。
本発明のアルコール溶液中の炭素数１〜４のアルコールの含有量は、８０〜９９．９９９質量％が好ましく、９５〜９９．９９８質量％がより好ましく、９８〜９９．９９５質量％が更に好ましく、９９〜９９．９９質量％がより更に好ましい。
また、本発明のアルコール溶液には、必要により公知の粘着性付与剤、炭素数１〜４のアルコール以外の揮発性の溶剤、水、有機又は無機顔料、染料、有機又は無機の紛体等を含有することができる。
The content of the pressure-sensitive adhesive in the alcohol solution of the present invention is preferably 0.001 to 20% by mass, more preferably 0.002 to 5% by mass from the viewpoint of adhesive strength and ease of coating film formation operation. 0.005 to 2 mass% is more preferable, and 0.01 to 1 mass% is still more preferable.
80-99.999 mass% is preferable, as for content of C1-C4 alcohol in the alcohol solution of this invention, 95-99.998 mass% is more preferable, and 98-99.995 mass% is still more preferable. 99 to 99.99% by mass is even more preferable.
Further, the alcohol solution of the present invention contains a known tackifier, a volatile solvent other than an alcohol having 1 to 4 carbon atoms, water, an organic or inorganic pigment, a dye, an organic or inorganic powder, if necessary. can do.
本発明のアルコール溶液は、ポリエステルフィルム等のプラスチックフィルム、紙、不織布、織布等の多孔質材料、金属箔等の基材の片面または両面に塗着ないし転写して、シート状やテープ状などの形態の粘着シートとして用いることができる。本発明のアルコール溶液を用いた粘着シートは、野菜や生花の結束用等として有用である。
更に、本発明のアルコール溶液は、毛髪等にスプレーすることで毛髪セット剤として用いることができる。本発明のアルコール溶液を用いた毛髪セット剤は、粘着付与剤を必要とせず、自己選択的粘着性を有するので、強いセット力とべたつきが少ない良好な感触とを実現することができる。
The alcohol solution of the present invention is applied to or transferred to one or both sides of a base material such as a plastic film such as a polyester film, a porous material such as paper, non-woven fabric or woven fabric, or a metal foil, and is in the form of a sheet or tape. It can be used as an adhesive sheet of the form. The pressure-sensitive adhesive sheet using the alcohol solution of the present invention is useful for binding vegetables and fresh flowers.
Furthermore, the alcohol solution of the present invention can be used as a hair setting agent by spraying on hair or the like. Since the hair setting agent using the alcohol solution of the present invention does not require a tackifier and has self-selective adhesiveness, a strong setting force and a good feel with little stickiness can be realized.
以下の例において、本発明のポリマーの重量平均分子量は次に示す方法で測定した。
＜重量平均分子量の測定方法＞
重量平均分子量は、ゲル濾過クロマトグラフィー（ＧＰＣ）により、下記条件で測定した。ポリスチレン標準サンプルで分子量は校正し、重量平均分子量を決定した。
In the following examples, the weight average molecular weight of the polymer of the present invention was measured by the following method.
<Measurement method of weight average molecular weight>
The weight average molecular weight was measured by gel filtration chromatography (GPC) under the following conditions. The molecular weight was calibrated with a polystyrene standard sample, and the weight average molecular weight was determined.
ＧＰＣの測定条件
・サンプル濃度：ポリマー５ｍｇ／ｍＬ（クロロホルム溶液）
・サンプル注入量：１００μＬ
・溶離液：クロロホルム
・流速：１．０ｍＬ／ｍｉｎ
・測定温度：４０℃
・カラム：商品名「Ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０４Ｌ」（昭和電工株式会社製）
・検出器：示差屈折計（ＧＰＣ装置 商品名「ＨＬＣ−８２２０ＧＰＣ」（東ソー株式会社）に付属）
・ポリスチレン標準サンプル：「ＴＳＫｓｔａｎｄａｒｄ ＰＯＬＹＳＴＹＲＥＮＥ Ｆ−１０」（分子量１０．２万）、「Ｆ−１」（１．０２万）、「Ａ−１０００」（８７０）（以上、東ソー株式会社）、及び「ＰＯＬＹＳＴＹＲＥＮＥ ＳＴＡＮＤＡＲＤ」（分子量９０万、３万：西尾工業株式会社）
GPC measurement conditions and sample concentration: polymer 5 mg / mL (chloroform solution)
Sample injection volume: 100 μL
-Eluent: Chloroform-Flow rate: 1.0 mL / min
・ Measurement temperature: 40 ℃
Column: Trade name “Shodex GPC K-804L” (manufactured by Showa Denko KK)
Detector: Differential refractometer (attached to GPC device trade name “HLC-8220GPC” (Tosoh Corporation))
Polystyrene standard samples: “TSK standard POLYSYRENE F-10” (molecular weight 102,000), “F-1” (1.020,000), “A-1000” (870) (above, Tosoh Corporation), and “ "POLYSTYRENE STANDARD" (Molecular weight 900,000, 30,000: Nishio Kogyo Co., Ltd.)
合成例１
撹拌器、還流冷却管、滴下漏斗を取り付けた反応容器内を窒素置換し、６５℃に昇温した。反応溶液としてエチルアクリレート（和光純薬工業株式会社製）１０１．２３ｇ、２−ブタノン（和光純薬工業株式会社製）６６．３７ｇ、２，２'−アゾビス(２，４-ジメチルバレロニトリル) （Ｖ−６５Ｂ、和光純薬工業株式会社製）０．１９ｇ、の混合溶液を滴下漏斗に入れ、このうち２０ｍＬを反応容器内に一度に添加した。続いて、滴下漏斗中の残りの混合溶液を反応容器中に２時間半かけて連続滴下し、更に６５℃で２時間撹拌し、反応させた。反応後の溶液を室温まで放冷した後、２−ブタノン２００ｍＬを加えて撹拌し、この均一溶液をｎ−ヘキサン４Ｌ（和光純薬工業株式会社製）中に滴下した。生じた白色沈殿を８０℃、２０ｋＰａで１２時間減圧乾燥し、ポリエチルアクリレート（重量平均分子量：１６２０００、重量平均分子量１万以下の成分：０．８４質量％）を得た。これをポリマー１とする。
Synthesis example 1
The inside of the reaction vessel equipped with a stirrer, a reflux condenser, and a dropping funnel was replaced with nitrogen, and the temperature was raised to 65 ° C. As reaction solution, 101.23 g of ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 66.37 g of 2-butanone (manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2,4-dimethylvaleronitrile) ( V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) 0.19 g was placed in a dropping funnel, and 20 mL of this was added to the reaction vessel at once. Subsequently, the remaining mixed solution in the dropping funnel was continuously dropped into the reaction vessel over 2 hours and a half, and further stirred at 65 ° C. for 2 hours to be reacted. After allowing the solution after the reaction to cool to room temperature, 200 mL of 2-butanone was added and stirred, and this homogeneous solution was dropped into 4 L of n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.). The resulting white precipitate was dried under reduced pressure at 80 ° C. and 20 kPa for 12 hours to obtain polyethyl acrylate (a component having a weight average molecular weight of 162000 and a weight average molecular weight of 10,000 or less: 0.84% by mass). This is polymer 1.
合成例２
反応溶液としてエチルアクリレート５０．０ｇ、アセトン１１６．７ｇ、２,２’−アゾビス(２,４-ジメチルバレロニトリル)０．１９ｇの混合溶液を用い、反応容器内の温度として窒素置換した後に５７℃に昇温し、反応温度を５７℃とし、反応後の溶液に加える溶媒をアセトン２００ｍＬとしたこと以外は、合成例１と同様の手法により、ポリエチルアクリレート（重量平均分子量：３０１０００、重量平均分子量１万以下の成分：０．６８質量％）を得た。これをポリマー２とする。
Synthesis example 2
As a reaction solution, a mixed solution of 50.0 g of ethyl acrylate, 116.7 g of acetone, and 0.19 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was used. The reaction temperature was changed to 57 ° C., and polyethyl acrylate (weight average molecular weight: 301000, weight average molecular weight was obtained in the same manner as in Synthesis Example 1 except that the solvent added to the solution after the reaction was 200 mL of acetone. 10,000 or less component: 0.68 mass%) was obtained. This is polymer 2.
比較合成例１
反応溶液としてエチルアクリレート２５．０ｇ、アセトン２２５．０ｇ、２,２’−アゾビス(２,４-ジメチルバレロニトリル)０．２９ｇの混合溶液を用いたこと以外は、合成例２と同様の手法により、ポリエチルアクリレート（重量平均分子量：６５０００、重量平均分子量１万以下の成分：３．１質量％）を得た。これを比較ポリマー１とする。
Comparative Synthesis Example 1
The same procedure as in Synthesis Example 2 was used except that a mixed solution of 25.0 g of ethyl acrylate, 225.0 g of acetone, and 0.29 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was used as the reaction solution. , Polyethyl acrylate (weight-average molecular weight: 65,000, weight-average molecular weight of 10,000 or less component: 3.1 mass%) was obtained. This is designated as Comparative Polymer 1.
比較合成例２
反応溶液として、エチルアクリレート７５．０ｇ、アセトン１１２．５ｇ、２,２’-アゾビス(２,４-ジメチルバレロニトリル)０．２０ｇの混合溶液を用いたこと以外は、合成例２と同様の手法により、ポリエチルアクリレート（重量平均分子量：４４７０００、重量平均分子量１万以下の成分：０．０５３質量％）を得た。これを比較ポリマー２とする。
Comparative Synthesis Example 2
The same procedure as in Synthesis Example 2 except that a mixed solution of 75.0 g of ethyl acrylate, 112.5 g of acetone, and 0.20 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was used as the reaction solution. Thus, polyethyl acrylate (weight average molecular weight: 447000, component having a weight average molecular weight of 10,000 or less: 0.053% by mass) was obtained. This is designated as Comparative Polymer 2.
比較合成例３
反応溶液としてブチルアクリレート４０．０ｇ、アセトン９３．３ｇ、２,２’−アゾビス（２，４-ジメチルバレロニトリル）０．１５ｇの混合溶液を用い、反応後の溶液を滴下する再沈殿溶媒をメタノール／水（体積比）＝１の混合溶液４Ｌとしたこと以外は、合成例２と同様の手法により、ポリブチルアクリレート（重量平均分子量：２７７０００、重量平均分子量１万以下の成分：０．１０質量％）を得た。これを比較ポリマー３とする。
Comparative Synthesis Example 3
A mixed solution of 40.0 g of butyl acrylate, 93.3 g of acetone, and 0.15 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was used as the reaction solution, and the reprecipitation solvent to which the solution after the reaction was added dropwise was methanol. / Polybutyl acrylate (weight average molecular weight: 277000, component having a weight average molecular weight of 10,000 or less: 0.10 mass) in the same manner as in Synthesis Example 2 except that the mixed solution is 4 L with water (volume ratio) = 1. %). This is designated as Comparative Polymer 3.
合成例３
合成例１で得られたポリマー１と比較合成例１で得られた比較ポリマー１を９：１（質量比）で混合してアセトン中に溶解し乾燥した。得られたポリマーをポリマー３とする（重量平均分子量：１５５０００、重量平均分子量１万以下の成分：２．４質量％）。
Synthesis example 3
The polymer 1 obtained in Synthesis Example 1 and the comparative polymer 1 obtained in Comparative Synthesis Example 1 were mixed at 9: 1 (mass ratio), dissolved in acetone and dried. The obtained polymer is referred to as "polymer 3" (component having a weight average molecular weight of 155,000 and a weight average molecular weight of 10,000 or less: 2.4 mass%).
実施例１〜３、及び比較例１〜３
合成例１〜３で得られたポリマー１〜３、及び比較合成例１〜３で得られた比較ポリマー１〜３について、下記方法でエタノール溶解性及び自己選択的粘着性を評価した。結果を表１に示す。
Examples 1-3 and Comparative Examples 1-3
About the polymers 1-3 obtained by the synthesis examples 1-3 and the comparison polymers 1-3 obtained by the comparative synthesis examples 1-3, ethanol solubility and self-selective adhesiveness were evaluated by the following method. The results are shown in Table 1.
＜エタノール溶解性の評価方法＞
ポリマーをエタノール中に０．０１質量％加えて撹拌し、この溶液の下記条件における透過率を測定した。この透過率が高いほど溶解性が高いことを示す。
装 置：ＵＶ可視光分光光度計ＵＶ-２５５０（株式会社島津製作所製）
測定モード：透過率
測定波長（λ）：６６０ ｎｍ
光路長：１ ｃｍ
試 料：０．０１質量％エタノール溶液
<Ethanol solubility evaluation method>
The polymer was added in 0.01% by mass in ethanol and stirred, and the transmittance of this solution under the following conditions was measured. The higher the transmittance, the higher the solubility.
Apparatus: UV-visible light spectrophotometer UV-2550 (manufactured by Shimadzu Corporation)
Measurement mode: transmittance Measurement wavelength (λ): 660 nm
Optical path length: 1 cm
Sample: 0.01 mass% ethanol solution
＜自己選択的粘着性の評価方法＞
（１）自己粘着性評価：直径約１０ｍｍ球状のバルクのポリマーを２つ作製し、それらを指で接触させ、１００ｇ重程度の力で３秒間押し付けた。同じ力で再び引き離したときの界面の消失しやすさ（自己接着しやすさ）を目視により次の５段階で評価し、その５回平均を評価値とした。このとき、完全に接着してポリマー同士の界面がなくなっていたものを評価５とし、全く接着せず引き離せたものを評価１とした。
５：自己接着する ４：やや自己接着しやすい ３：どちらでもない
２：やや自己接着しにくい １：自己接着しない
<Method for evaluating self-selective adhesiveness>
(1) Self-adhesive evaluation: Two bulk polymers having a spherical shape with a diameter of about 10 mm were prepared, brought into contact with a finger, and pressed with a force of about 100 g for 3 seconds. The ease of disappearance of the interface (ease of self-adhesion) when separated again with the same force was visually evaluated in the following five stages, and the average of the five times was used as the evaluation value. At this time, a case where the polymer was completely adhered and the interface between the polymers disappeared was evaluated as 5, and a case where the polymer was not adhered at all and separated was evaluated as Evaluation 1.
5: Self-adhesive 4: Slightly self-adhesive 3: None Neither 2: Slightly difficult to self-adhere 1: Not self-adhesive
（２）べたつき評価：バルクのポリマーを指で触ったときのべたつきを触感により次の５段階で評価し、その５人のパネラーによる平均を評価値とした。
５：べたつかない ４：ややべたつかない ３：どちらでもない
２：ややべたつく １：べたつく
(2) Stickiness evaluation: Stickiness when a bulk polymer was touched with a finger was evaluated by tactile sensation in the following five stages, and an average of the five panelists was used as an evaluation value.
5: Not sticky 4: Slightly sticky 3: None Neither 2: Slightly sticky 1: Sticky
（３）自己選択的粘着性評価：上記（１）、（２）の評価で自己粘着性が高く他着性が低い、具体的には（１）自己粘着性及び（２）べたつきの両評価値が３．５以上であるサンプルを自己選択的粘着性があると判断した。 (3) Self-selective adhesive evaluation: high self-adhesiveness and low adherence in the evaluations (1) and (2) above. Specifically, both (1) self-adhesive and (2) stickiness evaluation Samples with a value of 3.5 or higher were judged to have self-selective tackiness.
表１及び表２から、実施例１〜３で得られた本発明に属する粘着剤は、比較例１〜３で得られた粘着剤と比較して、自己選択的粘着性を有し、かつ低級アルコールに対する溶解性が高いことができることがわかる。 From Table 1 and Table 2, the pressure-sensitive adhesives belonging to the present invention obtained in Examples 1 to 3 have self-selective adhesiveness compared to the pressure-sensitive adhesives obtained in Comparative Examples 1 to 3, and It turns out that the solubility with respect to a lower alcohol can be high.
Claims (7)
〔式中、Ｒは水素原子、アルカリ金属原子又は炭素数１〜１２の直鎖又は分岐の炭化水素基であって、ポリマー中複数のＲは互いに同一又は異なって、ポリマー分子中におけるＲの炭素数の数平均値は１〜３である。〕 The content of the structural unit represented by the following general formula (1) is 50 to 100% by mass, the weight average molecular weight is 150 to 400,000, and the content of the polymer having a weight average molecular weight of 10,000 or less is 3 A pressure-sensitive adhesive comprising a polymer having a mass% or less.
[In the formula, R is a hydrogen atom, an alkali metal atom or a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R in the polymer are the same or different from each other, The number average value of the numbers is 1-3. ]
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| JPS5263228A (en) * | 1975-11-20 | 1977-05-25 | Toyobo Co Ltd | Adhesive compositions |
| JPS6042319A (en) * | 1983-07-25 | 1985-03-06 | ロレアル | Cosmetic composition |
| JPH11255812A (en) * | 1998-03-13 | 1999-09-21 | Nippon Shokubai Co Ltd | Ultra high molecular weight polymer with narrow molecular weight distribution, its manufacture and usage |
| JP2005220246A (en) * | 2004-02-06 | 2005-08-18 | Toyo Ink Mfg Co Ltd | Adhesive, and tape or sheet using the same |
| JP2006183034A (en) * | 2004-12-02 | 2006-07-13 | Nitto Denko Corp | Pressure-sensitive adhesive for optical film, pressure-sensitive adhesive layer for optical film, its manufacturing method, pressure-sensitive adhesive optical film and image display device |
| JP2008222814A (en) * | 2007-03-12 | 2008-09-25 | Nichiban Co Ltd | Self-adhesion adhesive and self-adhesion adhesive tape using it |
| CN102477267A (en) * | 2010-11-23 | 2012-05-30 | 上海恩意材料科技有限公司 | Solution-type acrylate adhesive |
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2011
- 2011-12-27 JP JP2011286942A patent/JP5973722B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5263228A (en) * | 1975-11-20 | 1977-05-25 | Toyobo Co Ltd | Adhesive compositions |
| JPS6042319A (en) * | 1983-07-25 | 1985-03-06 | ロレアル | Cosmetic composition |
| JPH11255812A (en) * | 1998-03-13 | 1999-09-21 | Nippon Shokubai Co Ltd | Ultra high molecular weight polymer with narrow molecular weight distribution, its manufacture and usage |
| JP2005220246A (en) * | 2004-02-06 | 2005-08-18 | Toyo Ink Mfg Co Ltd | Adhesive, and tape or sheet using the same |
| JP2006183034A (en) * | 2004-12-02 | 2006-07-13 | Nitto Denko Corp | Pressure-sensitive adhesive for optical film, pressure-sensitive adhesive layer for optical film, its manufacturing method, pressure-sensitive adhesive optical film and image display device |
| JP2008222814A (en) * | 2007-03-12 | 2008-09-25 | Nichiban Co Ltd | Self-adhesion adhesive and self-adhesion adhesive tape using it |
| CN102477267A (en) * | 2010-11-23 | 2012-05-30 | 上海恩意材料科技有限公司 | Solution-type acrylate adhesive |
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