JP6996077B2 - Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive - Google Patents
Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive Download PDFInfo
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- JP6996077B2 JP6996077B2 JP2016190628A JP2016190628A JP6996077B2 JP 6996077 B2 JP6996077 B2 JP 6996077B2 JP 2016190628 A JP2016190628 A JP 2016190628A JP 2016190628 A JP2016190628 A JP 2016190628A JP 6996077 B2 JP6996077 B2 JP 6996077B2
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- HPQKNJHVWUWAOR-QAMXDBPSSA-N C[C@@H](CC[C@H]([C@@](C)(CCC1)C(CC2)[C@@]1(C)C(O)=O)C2=C)CC(O)=O Chemical compound C[C@@H](CC[C@H]([C@@](C)(CCC1)C(CC2)[C@@]1(C)C(O)=O)C2=C)CC(O)=O HPQKNJHVWUWAOR-QAMXDBPSSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、粘着付与樹脂、該粘着付与樹脂を含む粘・接着剤、及び該粘着付与樹脂を含むホットメルト接着剤に関する。 The present invention relates to a tackifier resin, a sticky / adhesive containing the tackifier resin, and a hot melt adhesive containing the tackifier resin.
本明細書において「粘・接着剤」とは粘着剤及び/又は接着剤を、「ホットメルト接着剤」とは、支持体に溶融状態で塗付され冷却固化状態で接着層を形成する接着剤を意味する(以上、JIS K 6800参照)。 In the present specification, the "adhesive / adhesive" is an adhesive and / or an adhesive, and the "hot melt adhesive" is an adhesive that is applied to a support in a molten state to form an adhesive layer in a cooled and solidified state. Means (see JIS K 6800 above).
ロジンとポリオールの反応物であるロジンエステルは、粘着付与樹脂としてホットメルト接着剤や溶剤型粘・接着剤、エマルジョン型粘・接着剤等において賞用されている(特許文献1~3を参照)。 The rosin ester, which is a reaction product of rosin and polyol, has been used as a tackifier resin in hot melt adhesives, solvent-based adhesives / adhesives, emulsion-type adhesives / adhesives, etc. (see Patent Documents 1 to 3). ..
それら粘・接着剤は、高温条件で使用されることがあり、その場合、ロジンエステルとしては高軟化点のものが使用される。そうしたものとしては、例えば、フマル酸等のα,β不飽和カルボン酸をロジンに反応させてなる所謂強化ロジンとポリオールとの反応物(強化ロジンエステル)が知られている(特許文献4及び5を参照)。 These adhesives / adhesives may be used under high temperature conditions, and in that case, those having a high softening point are used as the rosin ester. As such, for example, a reaction product of a so-called fortified rosin and a polyol (enhanced rosin ester) obtained by reacting an α, β unsaturated carboxylic acid such as fumaric acid with rosin is known (Patent Documents 4 and 5). See).
一方、従来の強化ロジンエステルは、ホットメルト接着剤の粘着付与樹脂として使用する場合、ベース樹脂、特にエチレンー酢酸ビニル共重合体との相溶性が不十分な場合があった。また、該ロジンエステルを含むホットメルト接着剤は、加熱時に濁りや皮張りが生ずるなど加熱安定性が不十分な場合や、溶融粘度が高いため塗工作業性が十分でない場合があった。 On the other hand, when the conventional reinforced rosin ester is used as a tackifier resin for a hot melt adhesive, the compatibility with the base resin, particularly the ethylene-vinyl acetate copolymer, may be insufficient. Further, the hot melt adhesive containing the rosin ester may have insufficient heating stability such as turbidity or peeling during heating, or may not have sufficient coating workability due to its high melt viscosity.
本発明の課題は、ホットメルト接着剤の粘着付与樹脂として使用した場合において、ベース樹脂との相溶性が良好であり、かつ、該ホットメルトの溶融粘度を低下させ、かつ、その加熱安定性をも向上させ得る、新規なロジンエステルタイプの粘着付与樹脂を提供することにある。 The subject of the present invention is that when used as a tackifier resin for a hot melt adhesive, the compatibility with the base resin is good, the melt viscosity of the hot melt is lowered, and the heating stability thereof is improved. It is an object of the present invention to provide a novel rosin ester type tackifier resin which can be improved.
本発明者は、従来の強化ロジンエステルは、例えば下記構造で示される多塩基樹脂酸を多く含んでおり、これが分岐点となって非常に高分子量化されているため、ホットメルト接着剤のベース樹脂と相溶し難いと考えた。 According to the present inventor, the conventional reinforced rosin ester contains a large amount of the polybasic resin acid shown in the following structure, for example, which serves as a branch point and has a very high molecular weight, so that it is the base of the hot melt adhesive. I thought it would be difficult to dissolve with the resin.
強化ロジンエステルの分子量を下げるには、α,β不飽和カルボン酸の使用量を減らし、強化の程度を低くすればよいが、そのような低分子量の強化ロジンエスルはホットメルト剤の溶融粘度を著しく低下させ、加熱安定性も悪化させる。 In order to reduce the molecular weight of the fortified rosin ester, the amount of α, β unsaturated carboxylic acid used may be reduced to reduce the degree of fortification, but such a low molecular weight fortified rosin esul significantly increases the melt viscosity of the hot melt agent. It lowers and also deteriorates heating stability.
そこで本発明者は、α,β不飽和カルボン酸を使用せずとも高分子量化を達成できる原料ロジンについて検討を重ねた結果、反応性に富む二塩基性樹脂酸を含むロジンを用いることによって、所期の効果を奏する粘着付与樹脂が得られることを見出した。 Therefore, as a result of repeated studies on a raw material rosin that can achieve high molecular weight without using α, β unsaturated carboxylic acid, the present inventor has decided to use a rosin containing a highly reactive dibasic resin acid. It has been found that a tackifier resin having the desired effect can be obtained.
すなわち本発明は、二塩基性ジテルペンカルボン酸を含むロジン類(a1)及びポリオール(a2)を反応成分とするロジンエステル(A)を含有する粘着付与樹脂、並びに該粘着付与樹脂とベース樹脂とを含有する粘・接着剤及びホットメルト接着剤に関する。 That is, the present invention comprises a tackifier resin containing rosins (a1) containing a diterpene carboxylic acid and a rosin ester (A) containing a polyol (a2) as reaction components, and the tackifier resin and a base resin. Concerning the viscous / adhesive and hot melt adhesive contained.
本発明の粘着付与樹脂たるロジンエステルは、二塩基性ジテルペンカルボン酸を含むため、α,β不飽和カルボン酸で変性しなくても従来の強化ロジンエステルと同等以上の性能を奏する。 Since the rosin ester, which is a tackifier resin of the present invention, contains a bibasic diterpene carboxylic acid, it exhibits performance equal to or higher than that of the conventional enhanced rosin ester without being modified with α, β unsaturated carboxylic acid.
具体的には、本発明の粘着付与樹脂は、ホットメルト接着剤用のベース樹脂、特にエチレンー酢酸ビニル共重合体との相溶性が良好であり、均質で透明なホットメルト接着剤を与える。また、本発明に係るホットメルト接着剤は、溶融粘度が相対的に小さいため塗工作業性良好であり、さらに加熱安定性も良好であるため、長時間加熱しても濁りや皮張りが生じ難い。また、当該ホットメルト接着剤は耐熱保持力にも優れる。 Specifically, the tackifier resin of the present invention has good compatibility with a base resin for a hot melt adhesive, particularly an ethylene-vinyl acetate copolymer, and provides a homogeneous and transparent hot melt adhesive. Further, since the hot melt adhesive according to the present invention has a relatively small melt viscosity, it has good coating workability and also has good heating stability, so that turbidity and skinning occur even when heated for a long time. hard. In addition, the hot melt adhesive is also excellent in heat resistance holding power.
本発明の粘着付与樹脂は、ホットメルト接着剤用途で好適であるが、溶剤型粘・接着剤やエマルジョン型粘・接着剤等にも好適である。 The tackifier resin of the present invention is suitable for hot melt adhesive applications, but is also suitable for solvent-type adhesives / adhesives, emulsion-type adhesives / adhesives, and the like.
本発明の粘着付与樹脂(以下、成分ともいう。)は、下記構造式で示される二塩基性ジテルペンカルボン酸を含むロジン類(a1)(以下、(a1)成分ともいう。)、ポリオール(a2)を反応成分とするロジンエステル(A)(以下、(A)成分ともいう。)を含有する組成物である。 The tackifier resin (hereinafter, also referred to as a component) of the present invention is a rosin (a1) (hereinafter, also referred to as a component (a1)) containing a dibasic diterpene carboxylic acid represented by the following structural formula, and a polyol (a2). ) Is a reaction component, and is a composition containing a rosin ester (A) (hereinafter, also referred to as a component (A)).
二塩基性ジテルペンカルボン酸は、その立体異性構造により、ジヒドロアガト酸、オリベリ酸、エペルエンジカルボン酸及びピニフォリン酸に分類できる。以下に、ジヒドロアガト酸の非限定的な構造を示す。 The dibasic diterpene carboxylic acid can be classified into dihydroagatoic acid, olibergic acid, eperenedicarboxylic acid and piniphoric acid according to its stereoisomeric structure. The non-limiting structure of dihydroagatoic acid is shown below.
該二塩基性ジテルペンカルボン酸は、一級カルボキシル基が柔軟なアルキル鎖を介して脂環骨格に結合した特異な構造を有する。また、該一級カルボキシル基は反応性が高く、後述の(a2)と容易に反応し、高分子量ポリエステルを容易に形成する。該ポリエステルの非限定的な構造を以下に示す。 The bibasic diterpene carboxylic acid has a unique structure in which a primary carboxyl group is attached to an alicyclic skeleton via a flexible alkyl chain. Further, the primary carboxyl group has high reactivity and easily reacts with (a2) described later to easily form a high molecular weight polyester. The non-limiting structure of the polyester is shown below.
(A)成分は、そうした特徴的な分子骨格のポリエステルを含むため、強化変性されていなくても従来の強化ロジンエステルと同等以上の作用効果を奏するのであろうと推察される。 Since the component (A) contains a polyester having such a characteristic molecular skeleton, it is presumed that the component (A) exerts an action effect equal to or higher than that of the conventional reinforced rosin ester even if it is not reinforced and modified.
(a1)成分における前記二塩基性ジテルペンカルボン酸の含有量は特に限定されないが、該カルボン酸の含有量が少なすぎると(A)成分の軟化点が低くなって、前記耐熱保持力が低下する傾向にある。また、該カルボン酸の含有量が多すぎると(A)成分の分子量が高くなって、前記相溶性及び加熱安定性が悪化し、前記溶融粘度も相対的に高くなって塗工作業性が悪化する傾向にある。耐熱保持力、相溶性、加熱安定性及び溶融粘度のバランスの観点より、二塩基性ジテルペンカルボン酸の含有量は通常20重量%未満、好ましくは1~15重量%程度、より好ましくは3~13重量%程度であるのがよい。 The content of the diterpene carboxylic acid in the component (a1) is not particularly limited, but if the content of the carboxylic acid is too small, the softening point of the component (A) is lowered and the heat-resistant holding power is lowered. There is a tendency. Further, if the content of the carboxylic acid is too large, the molecular weight of the component (A) becomes high, the compatibility and the heating stability deteriorate, and the melt viscosity also becomes relatively high, and the coating workability deteriorates. Tend to do. From the viewpoint of heat retention, compatibility, heat stability and melt viscosity balance, the content of diterpene carboxylic acid is usually less than 20% by weight, preferably about 1 to 15% by weight, more preferably 3 to 13. It should be about% by weight.
(a1)成分としては、例えば、以下の態様が挙げられる。 Examples of the component (a1) include the following aspects.
(ア):二塩基性ジテルペンカルボン酸をもともと含むロジン
(イ):(ア)成分と、二塩基性ジテルペンカルボン酸を含まないロジンとを組み合わせてなるロジン
(ウ):ジヒドロアガト酸を、二塩基性ジテルペンカルボン酸を含まないロジン及び/又は(ア)成分に組み合わせてなるロジン
(A): Rosin originally containing diterpene carboxylic acid (b): Rosin consisting of a combination of the component (a) and rosin not containing diterpene carboxylic acid (c): Dihydroagatoic acid. A rosin that does not contain basic diterpene carboxylic acid and / or a rosin that is combined with the component (a).
(ア)成分としては、二塩基性ジテルペンカルボン酸を含むロジンであれば、産地及び松種は問わない。例えば、インドネシア産のロジンやベトナム産のロジンには二塩基性ジテルペンカルボン酸が比較的多く含まれている。特に、インドネシア産やベトナム産のメルクシ松(Pinus merkusii)由来のロジン(ガムロジン、トール油ロジン、ウッドロジン等)には、専らジヒドロアガト酸が含まれる。また、該ロジンの水素化物や不均化物も使用できる。 As the component (a), as long as it is a rosin containing a diterpene carboxylic acid, the place of origin and the pine species do not matter. For example, Indonesian rosin and Vietnamese rosin contain a relatively large amount of diterpene carboxylic acid. In particular, rosins (gamrosin, tall oil rosin, wood rosin, etc.) derived from Pinus merkusii from Indonesia and Vietnam contain dihydroagatoic acid exclusively. Further, a hydride or an attenuated rosin of the rosin can also be used.
(ア)成分は、各種公知の方法で精製してもよい。具体的には、例えば、蒸留、再結晶及び抽出等の操作が挙げられる。蒸留の条件は特に限定されず、通常、温度が200~300℃程度、及び圧力が130~1300Pa程度である。再結晶は、(ア)成分をベンゼンやトルエン、キシレン、クロロホルム、低級アルコール、アセトン、酢酸エチル等の良溶媒に溶解させた後、該良溶媒を留去して濃厚な溶液となし、該溶液に、n-ヘキサンやn-ヘプタン、シクロヘキサン、イソオクタン等の貧溶媒を添加すればよい。抽出は、(ア)成分をアルカリ水溶液となし、不溶性の不ケン化物を適当な溶媒を用いて抽出した後、水層を中和すればよい。 The component (a) may be purified by various known methods. Specific examples thereof include operations such as distillation, recrystallization and extraction. The distillation conditions are not particularly limited, and usually, the temperature is about 200 to 300 ° C. and the pressure is about 130 to 1300 Pa. For recrystallization, the component (a) is dissolved in a good solvent such as benzene, toluene, xylene, chloroform, lower alcohol, acetone, ethyl acetate, etc., and then the good solvent is distilled off to form a concentrated solution. A poor solvent such as n-hexane, n-heptane, cyclohexane, or isooctane may be added to the solution. For extraction, the component (a) may be an alkaline aqueous solution, an insoluble unkenzide may be extracted with an appropriate solvent, and then the aqueous layer may be neutralized.
(イ)成分をなす、二塩基性ジテルペンカルボン酸を含まないロジンとしては、各種公知のものを特に限定無く使用することができる。具体的には、例えば、ガムロジン、トール油ロジン、ウッドロジンなどの天然ロジンや、天然ロジンを精製して得られる精製ロジン、天然ロジンを水素化反応させて得られる水素化ロジン、天然ロジンを不均化反応させて得られる不均化ロジン等が挙げられる。 As the rosin containing no diterpene carboxylic acid, which is a component of (a), various known rosins can be used without particular limitation. Specifically, for example, natural rosins such as gum rosin, tall oil rosin, and wood rosin, purified rosins obtained by purifying natural rosins, hydrides obtained by hydrogenating natural rosins, and natural rosins are non-uniform. Examples thereof include disproportionate rosin obtained by a chemical reaction.
(ウ)成分をなす二塩基性ジテルペンカルボン酸は、例えば、特開昭51-131899号公報に記載の方法で調成可能である。 The diterpene carboxylic acid constituting the component (c) can be prepared, for example, by the method described in JP-A-51-131899.
(a1)成分には、二塩基性ジテルペンカルボン酸以外の樹脂酸として、例えば、アビエチン酸やデヒドロアビエチン酸が含まれる。それらの含有量は特に限定されないが、通常順に60重量%未満及び30重量%未満、好ましくは20~50重量%程度及び5重量%程度である。 The component (a1) includes, for example, abietic acid and dehydroabietic acid as resin acids other than the diterpene carboxylic acid dibasic. The content thereof is not particularly limited, but is usually less than 60% by weight and less than 30% by weight, preferably about 20 to 50% by weight and about 5% by weight.
(a1)成分における樹脂酸の含有量は、各種公知の手段で定量できる。例えば、ガスクロマトグラフィー(GC)を用い、定量目的の樹脂酸に由来するピーク面積を全樹脂酸のピーク面積で除することにより求め得る。 The content of the resin acid in the component (a1) can be quantified by various known means. For example, it can be obtained by using gas chromatography (GC) and dividing the peak area derived from the resin acid for quantification by the peak area of the total resin acid.
(a1)成分の物性は特に限定されないが、通常、軟化点が通常70~90℃程度であり、また、酸価が通常130~200mgKOH/g程度である。 The physical characteristics of the component (a1) are not particularly limited, but usually the softening point is usually about 70 to 90 ° C., and the acid value is usually about 130 to 200 mgKOH / g.
(a2)成分としては、各種公知のポリオールを使用できる。具体的には、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、ダイマージオール及び1,6-ヘキサンジオール等のジオールや、グリセリン、トリメチロールエタン及びトリメチロールプロパン等のトリオール、ペンタエリスリトール等のテトラオール、ジペンタエリスリトール等の5価以上のポリオール等が挙げられ、二種以上を併用できる。これらの中でも、(A)成分とベース樹脂の相溶性や、本発明に係る粘着剤・接着剤の性能を考慮すると、ジオール、トリオール及びテトラオールからなる群より選ばれる少なくとも一種が好ましい。 As the component (a2), various known polyols can be used. Specifically, for example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimerdiol and 1,6-hexanediol, and triols such as glycerin, trimethylolethane and trimethylolpropane, etc. Examples thereof include tetraol such as pentaerythritol, and polyols having a valence of 5 or more such as dipentaerythritol, and two or more thereof can be used in combination. Among these, at least one selected from the group consisting of diol, triol and tetraol is preferable in consideration of the compatibility between the component (A) and the base resin and the performance of the pressure-sensitive adhesive / adhesive according to the present invention.
(a2)成分の使用量は特に限定されないが、耐熱保持力等の粘・接着性能を特に考慮すると、(a1)成分の酸価(JIS K 0070。以下、酸価というときは同様。)と(a2)成分中水酸基価(JIS K 0070。以下、水酸価というときは同様。)との比率(OH/COOH)が通常0.5~4程度となる範囲であるのがよい。 The amount of the component (a2) used is not particularly limited, but the acid value of the component (a1) (JIS K 0070; hereinafter, the same applies hereinafter) is the same as the acid value of the component (a1), considering the adhesive performance such as heat retention. (A2) The ratio (OH / COOH) to the hydroxyl value in the component (JIS K 0070; hereinafter, the same applies to the water acid value) is usually in the range of about 0.5 to 4.
(A)成分の反応成分には、必要に応じて、各種公知のα,β不飽和カルボン酸類(a3)(以下、(a3)成分ともいう。)をふくめてよい。具体的には、例えば、アクリル酸及びメタクリル酸等のα,β不飽和モノカルボン酸、並びにフマル酸及び(無水)マレイン酸等のα,β不飽和ジカルボン酸等が挙げられ、二種以上を併用できる。 The reaction component of the component (A) may include various known α, β unsaturated carboxylic acids (a3) (hereinafter, also referred to as the component (a3)), if necessary. Specific examples thereof include α and β unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and α and β unsaturated dicarboxylic acids such as fumaric acid and (maleic anhydride) maleic acid. Can be used together.
(a3)成分の使用量は特に限定されないが、本発明の粘着付与樹脂とベースポリマーとの相溶性等を考慮すると、通常、(a1)成分中のアビエチン酸1モルに対して通常0.005~3モル程度、より好ましくは0.005~0.3モル程度となる範囲である。 The amount of the component (a3) used is not particularly limited, but in consideration of the compatibility between the tackifier resin of the present invention and the base polymer, etc., it is usually 0.005 with respect to 1 mol of abietic acid in the component (a1). It is in the range of about 3 mol, more preferably about 0.005 to 0.3 mol.
(A)成分としては、例えば、以下の態様が挙げられる。 Examples of the component (A) include the following aspects.
(A1):(a1)成分及び(a2)成分のエステル化物(ロジンエステル)
(A2):(A1)成分と(a3)成分のディールス・アルダー反応物(強化ロジンエステル)
(A3):(a1)成分及び(a3)成分のディールス・アルダー反応物と、(a2)成分とのエステル化物(強化ロジンエステル)
(A4):(a1)成分、(a2)成分及び(a3)成分の同時反応物(強化ロジンエステル)
(A1): Esterized product (rosin ester) of component (a1) and component (a2)
(A2): Diels-Alder reaction product (enhanced rosin ester) of component (A1) and component (a3)
(A3): An esterified product of the Diels-Alder reaction product of the components (a1) and (a3) and the component (a2) (enhanced rosin ester).
(A4): Simultaneous reaction product of (a1) component, (a2) component and (a3) component (enhanced rosin ester)
エステル化反応の条件は特に限定されず、例えば前記反応成分を、溶媒の存在下若しくは不存在下、及びエステル化触媒の存在下又は不存在下に、250~280℃程度及び1~8時間程度の条件で反応させればよい。該エステル化触媒としては、例えば、パラトルエンスルホン酸等の酸触媒や、水酸化カルシウム等のアルカリ金属の水酸化物、酸化カルシウム、酸化マグネシウム等の金属酸化物等が挙げられ、二種以上を併用できる。該エステル化反応は、常圧下、減圧下、加圧下及び窒素パージ下のいずれか又は組み合わせの雰囲気で行えばよい。 The conditions of the esterification reaction are not particularly limited, and for example, the reaction component is placed in the presence or absence of a solvent and in the presence or absence of an esterification catalyst at about 250 to 280 ° C. and about 1 to 8 hours. It suffices to react under the condition of. Examples of the esterification catalyst include acid catalysts such as paratoluenesulfonic acid, hydroxides of alkali metals such as calcium hydroxide, metal oxides such as calcium oxide and magnesium oxide, and two or more thereof. Can be used together. The esterification reaction may be carried out under normal pressure, reduced pressure, pressure and nitrogen purging, or in a combination atmosphere.
(A)成分の物性は特に限定されないが、(A)成分とベース樹脂の相溶性や、本発明に係粘・接着剤の加熱安定性、溶融粘度適性及び耐熱保持力のバランス等を考慮すると、重量平均分子量が通常800~4000程度であり、また、軟化点が通常70~180℃程度であり、また、酸価が1~100mgKOH/g程度である。 The physical properties of the component (A) are not particularly limited, but in consideration of the compatibility between the component (A) and the base resin, the heating stability of the adhesive / adhesive, the suitability for melt viscosity, the balance between heat retention and holding power, etc. in the present invention. The weight average molecular weight is usually about 800 to 4000, the softening point is usually about 70 to 180 ° C., and the acid value is about 1 to 100 mgKOH / g.
(A)成分には、架橋剤、防滑剤、防腐剤、防錆剤、pH調整剤、消泡剤(シリコン系消泡剤等)、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤、顔料、染料等の添加剤を含めてもよい。 The component (A) includes a cross-linking agent, an anti-slip agent, an antiseptic, an anti-rust agent, a pH adjuster, an antifoaming agent (silicone-based antifoaming agent, etc.), a thickener, a filler, an antioxidant, and a water resistant agent. , Additives such as film-forming aids, pigments and dyes may be included.
(A)成分は、後述の乳化剤の存在下でエマルジョンとなし、粘着付与樹脂として使用することもできる。 The component (A) can be used as a tackifier resin without forming an emulsion in the presence of an emulsifier described later.
本発明の粘・接着剤は、本発明の粘着付与樹脂とベース樹脂とを含有する組成物である。該組成物は、例えば、ホットメルト接着剤、溶剤型粘・接着剤、及びエマルジョン型の粘・接着剤として使用でき、特にホットメルト接着剤として好適である。 The adhesive / adhesive of the present invention is a composition containing the tackifier resin of the present invention and the base resin. The composition can be used as, for example, a hot melt adhesive, a solvent type adhesive / adhesive, and an emulsion type adhesive / adhesive, and is particularly suitable as a hot melt adhesive.
ベース樹脂としては、各種公知のものを特に制限なく使用できる。具体的には、例えば、エチレン系共重合体、合成ゴム系エラストマー、アクリル系共重合体、アクリル系重合体エマルジョン、ゴム系ラテックス等が挙げられ、本発明の粘・接着剤の前記利用態様に応じて適切なものを選択すればよい。ホットメルト接着剤用途では、エチレン系共重合体及び/又は合成ゴム系エラストマーが好ましい。 As the base resin, various known ones can be used without particular limitation. Specific examples thereof include ethylene-based copolymers, synthetic rubber-based elastomers, acrylic-based copolymers, acrylic-based polymer emulsions, rubber-based latexs, and the like. The appropriate one may be selected accordingly. Ethylene copolymers and / or synthetic rubber elastomers are preferred for hot melt adhesive applications.
エチレン系共重合体としては、例えば、エチレン-酢酸ビニル共重合体や、エチレン-アルキル(メタ)アクリレート共重合体が挙げられる。該アルキル(メタ)アクリレートとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸2-エチルヘキシル等を例示でき、二種以上を併用できる。 Examples of the ethylene-based copolymer include an ethylene-vinyl acetate copolymer and an ethylene-alkyl (meth) acrylate copolymer. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, and two or more thereof may be used in combination. can.
合成ゴム系エラストマーとしては、例えば、スチレン-イソプレン-スチレンブロック共重合体(SIS)、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-水添ブタジエン-スチレンブロック共重合体(SEBS)およびスチレン-エチレン・プロピレン-スチレン共重合体(SEPS)等が挙げられ、二種以上を併用できる。 Examples of the synthetic rubber-based elastomer include styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-hydrogenated butadiene-styrene block copolymer (SEBS) and Examples thereof include styrene-ethylene / propylene-styrene copolymer (SEPS), and two or more of them can be used in combination.
アクリル系共重合体(前記エチレン-アルキル(メタ)アクリレート共重合体を除く。)としては、例えば、(メタ)アクリル酸グリシジルや(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸、フマル酸、(無水)マレイン酸、イタコン酸等の活性水素基含有(メタ)アクリレートと前記アルキル(メタ)アクリレートとの共重合体等が挙げられ、二種以上を併用できる。 Examples of the acrylic copolymer (excluding the ethylene-alkyl (meth) acrylate copolymer) include glycidyl (meth) acrylic acid, 2-hydroxyethyl (meth) acrylic acid, (meth) acrylic acid, and fumal. Examples thereof include a copolymer of an active hydrogen group-containing (meth) acrylate such as acid, (anhydrous) maleic acid, and itaconic acid and the above-mentioned alkyl (meth) acrylate, and two or more thereof can be used in combination.
アクリル系共重合体エマルジョンとしては、前記アクリル系共重合体を乳化剤の存在下で乳化したものが挙げられる。該乳化剤としては、例えば、非反応性乳化剤及び/又は反応性乳化剤を使用できる。 Examples of the acrylic copolymer emulsion include those obtained by emulsifying the acrylic copolymer in the presence of an emulsifier. As the emulsifier, for example, a non-reactive emulsifier and / or a reactive emulsifier can be used.
非反応性乳化剤としては、例えば、ジアルキルスルホコハク酸エステル塩、アルカンスルホン酸塩、α-オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等のアニオン性乳化剤や、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル等のノニオン性乳化剤が挙げられる。 Examples of the non-reactive emulsifier include dialkyl sulfosuccinate ester salt, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate ester salt, polyoxyethylene styrylphenyl ether sulfosuccinate ester salt, and naphthalene sulfone. Anionic emulsifiers such as acid formalin condensates, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene alkyl ethers, polyoxyethylene styrylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, etc. Nonionic emulsifiers are mentioned.
反応性乳化剤としては、例えば、スルホン酸基、カルボキシル基などの親水基と、アルキル基、フェニル基などの疎水基を有する界面活性剤であって、分子中に炭素-炭素二重結合を有するものが挙げられる。該炭素-炭素二重結合としては、たとえば、(メタ)アリル基、1-プロペニル基、2-メチル-1-プロペニル基、ビニル基、イソプロペニル基、(メタ)アクリロイル基等の官能基が挙げられる。反応性乳化剤の具体例としては、たとえば、前記官能基を分子中に少なくとも1つ有するポリオキシエチレンアルキルエーテル、前記官能基を分子中に少なくとも1つ有するポリオキシエチレンフェニルエーテル、およびそれらのスルホコハク酸エステル塩や硫酸エステル塩が挙げられる。また、前記官能基を分子中に少なくとも1つ有するポリオキシエチレンアルキルフェニルエーテル、およびそのスルホコハク酸エステル塩、その硫酸エステル塩、そのリン酸エステル塩、その脂肪族若しくは芳香族カルボン酸塩が挙げられる。また、酸性リン酸(メタ)アクリル酸エステル系乳化剤、ロジングリシジルエステルアクリレートの酸無水物変性物(特開平4-256429号公報参照)、特開昭63-23725号公報、特開昭63-240931号公報、特開昭62-104802号公報に記載の乳化剤も使用できる。 The reactive emulsifier is, for example, a surfactant having a hydrophilic group such as a sulfonic acid group or a carboxyl group and a hydrophobic group such as an alkyl group or a phenyl group and having a carbon-carbon double bond in the molecule. Can be mentioned. Examples of the carbon-carbon double bond include functional groups such as (meth) allyl group, 1-propenyl group, 2-methyl-1-propenyl group, vinyl group, isopropenyl group and (meth) acryloyl group. Be done. Specific examples of the reactive emulsifier include, for example, a polyoxyethylene alkyl ether having at least one functional group in the molecule, a polyoxyethylene phenyl ether having at least one functional group in the molecule, and sulfosuccinic acid thereof. Examples include ester salts and sulfate ester salts. Examples thereof include polyoxyethylene alkylphenyl ether having at least one functional group in the molecule, a sulfosuccinic acid ester salt thereof, a sulfate ester salt thereof, a phosphoric acid ester salt thereof, and an aliphatic or aromatic carboxylate thereof. .. Further, an acid anhydride-based emulsifier for acidic phosphoric acid (meth) acrylic acid ester, an acid anhydride modified product of rosing lysidyl ester acrylate (see JP-A-4-256249), JP-A-63-23725, JP-A-63-240931. The emulsifier described in Japanese Patent Application Laid-Open No. 62-104802 can also be used.
ゴム系ラテックスとしては、例えば、天然ゴムラテックス、スチレン-ブタジエン共重合体ラテックス、クロロプレンラテックス等が挙げられ、二種以上を併用できる。 Examples of the rubber-based latex include natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex and the like, and two or more of them can be used in combination.
上記したもの以外のベース樹脂としては、例えば、ポリウレタン樹脂、液状ポリブタジエン、液状ポリイソブチレン、ポリビニルアセタール、ゼラチン、マンナン、デンプン等が挙げられ、二種以上を併用できる。 Examples of the base resin other than those described above include polyurethane resin, liquid polybutadiene, liquid polyisobutylene, polyvinyl acetal, gelatin, mannan, starch and the like, and two or more of them can be used in combination.
本発明の粘着付与樹脂と前記ベース樹脂の使用量は特に限定されないが、通常、前者100重量部(固形分換算)に対して後者が2~40重量部程度(固形分換算)である。 The amount of the tackifier resin and the base resin used in the present invention is not particularly limited, but is usually about 2 to 40 parts by weight (solid content equivalent) of the former 100 parts by weight (solid content conversion).
本発明の粘・接着剤には、他の粘着付与樹脂や、各種公知の有機溶剤、ワックス、架橋剤、及び前記添加剤を含めることができる。 The viscous / adhesive of the present invention may include other tackifier resins, various known organic solvents, waxes, cross-linking agents, and the above-mentioned additives.
他の粘着付与樹脂としては、例えば、ガムロジン、ウッドロジン及びトール油ロジン等の原料ロジン((a1)成分に該当するものを除く。)や、それらの精製物、水添物、重合物及び強化物等の変性ロジン、並びに該変性ロジンと前記(a2)成分及び/又は(a3)成分との反応物等が挙げられる。他にも、C9系石油樹脂、C5系石油樹脂及びC5/C9系石油樹脂、並びにそれらの水添物等の石油樹脂や、テルペン樹脂及びその水添物等が挙げられる。 Other tackifier resins include, for example, raw material rosins such as gum rosin, wood rosin and tall oil rosin (excluding those corresponding to the component (a1)), refined products thereof, hydrogenated products, polymers and reinforced products thereof. And the like, and a reaction product of the modified rosin with the component (a2) and / or the component (a3). In addition, C9-based petroleum resin, C5-based petroleum resin and C5 / C9-based petroleum resin, petroleum resins such as hydrogenated products thereof, terpene resin and hydrogenated products thereof and the like can be mentioned.
有機溶剤としては、例えば、アセトン、メチルエチルケトン、トルエン、ベンゼン、酢酸エチル、クロロホルム及びジメチルホルムアミド等が挙げられ、二種以上を併用できる。 Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, benzene, ethyl acetate, chloroform, dimethylformamide and the like, and two or more kinds can be used in combination.
ワックスとしては、例えば、蜜蝋、鯨蝋及びセラック蝋等の動物由来、カルナバ蝋、木蝋、米糠蝋及びキャンデリラワックス等の植物由来のワックス、パラフィンワックス及びマイクロクリスタリンワックス等の石油由来のワックス、並びにモンタンワックス及びオゾケライト等の鉱物由来のワックスが挙げられ、二種以上を併用できる。 Examples of the wax include animal-derived waxes such as beeswax, whale wax and cellac wax, plant-derived waxes such as carnauba wax, wood wax, rice bran wax and candelilla wax, petroleum-derived waxes such as paraffin wax and microcrystallin wax, and waxes. Examples include waxes derived from minerals such as montan wax and ozokerite, and two or more kinds can be used in combination.
架橋剤としては、例えば、ポリイソシアネート化合物、ポリアミン化合物、メラミン樹脂、尿素樹脂、エポキシ樹脂等の架橋剤を加えることにより、凝集力、耐熱性を更に向上させることもできる。これら架橋剤のなかでも、特にポリイソシアネート化合物を使用するのが好ましく、その具体例としては、1,6-ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、トリレンジイソシアネート、4,4-ジフェニルメタンジイソシアネート等の各種公知のものが挙げられる。更に本発明のアクリル系粘接着剤組成物は必要に応じて充填剤、酸化防止剤、紫外線吸収剤等を適宜使用しうる。また、本発明のアクリル系粘接着剤組成物は、本発明の目的を逸脱しない範囲で各種公知の粘着付与樹脂を併用することもできる。 As the cross-linking agent, for example, by adding a cross-linking agent such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, or an epoxy resin, the cohesive force and heat resistance can be further improved. Among these cross-linking agents, it is particularly preferable to use a polyisocyanate compound, and specific examples thereof include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4. -Various known substances such as diphenylmethane diisocyanate can be mentioned. Further, in the acrylic adhesive composition of the present invention, a filler, an antioxidant, an ultraviolet absorber and the like can be appropriately used as needed. Further, in the acrylic adhesive composition of the present invention, various known tackifier resins can be used in combination as long as the object of the present invention is not deviated.
以下、本発明を、実施例及び比較例を通じて詳細に説明するが、それらによって本発明の範囲が制限されないことはもとよりである。 Hereinafter, the present invention will be described in detail through Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited by them.
各例中、原料ロジン中のジヒドロアガト酸(DHAA)、アビエチン酸(AA)及びデヒドロアビエチン酸(DAA)の含有量は、以下のガスクロマトグラフ質量分析装置で測定した。測定には試料(ロジン類)0.005gをオンカラムメチル化剤(フェニルトリメチルアンモニウムヒドロキサイド(PTHA)0.2モルメタノール溶液、ジーエルサイエンス(株))0.5gに溶解させ、1μlをガスクロマトグラフ質量分析(GC/MS)に注入し、測定を行った。樹脂酸のメチルエステル体から、各含有量を決定した。使用装置はガスクロマトグラフ質量分析装置(製品名「Agilent6890」、「Agilent5973N」;Agilent technologies製)及び市販カラム(製品名「Advance-DS」、信和化工(株)製)である。 In each example, the contents of dihydroagatoic acid (DHAA), abietic acid (AA) and dehydroabietic acid (DAA) in the raw material rosin were measured by the following gas chromatograph mass spectrometer. For measurement, 0.005 g of a sample (rosins) was dissolved in 0.5 g of an on-column methylating agent (phenyltrimethylammonium hydroxyside (PTHA) 0.2 molmethanol solution, GL Sciences Co., Ltd.), and 1 μl was gas chromatograph mass. It was injected into the analysis (GC / MS) and measured. Each content was determined from the methyl ester form of the resin acid. The equipment used is a gas chromatograph mass spectrometer (product name "Agient6890", "Agient5973N"; manufactured by Agilent technologies) and a commercially available column (product name "Advance-DS", manufactured by Shinwa Kako Co., Ltd.).
各例中、ロジンエステルの重量平均分子量(Mw:ポリスチレン換算値)は以下の条件で求めた。
分析装置:HLC-8220(東ソー(株)製)
カラム:TSKgelSuperHM-L×3本
溶離液:テトラヒドロフラン
注入試料濃度:5mg/mL
流量:0.6mL/min
注入量:100μL
カラム温度:40℃
検出器:RI
In each example, the weight average molecular weight (Mw: polystyrene-equivalent value) of the rosin ester was determined under the following conditions.
Analyzer: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgelSuperHM-L x 3 Eluent: Tetrahydrofuran Injection Sample concentration: 5 mg / mL
Flow rate: 0.6 mL / min
Injection volume: 100 μL
Column temperature: 40 ° C
Detector: RI
各例中、ロジンエステルの軟化点(Sp(℃))は、JIS K 2531の環球法により測定した。 In each example, the softening point (Sp (° C.)) of the rosin ester was measured by the ring ball method of JIS K 2531.
1.粘着付与樹脂の合成1. 1. Synthesis of adhesive resin
製造例1
インドネシア産ガムロジン100部をキシレン100部に溶解し、室温で48%NaOHaq 5部、水33部を用いて1回抽出した。ついで水層(抽出液)を希塩酸で中和し遊離した樹脂酸をキシレン33部で抽出したのち、キシレンを200℃で留去してジヒドロアガト酸を90重量%含有する樹脂酸組成物(酸価290mgKOH/g)を得た。
Production Example 1
100 parts of Indonesian gumrosin was dissolved in 100 parts of xylene and extracted once with 5 parts of 48% NaOHaq and 33 parts of water at room temperature. Then, the aqueous layer (extract) was neutralized with dilute hydrochloric acid to extract the liberated resin acid with 33 parts of xylene, and then xylene was distilled off at 200 ° C. to contain 90% by weight of dihydroagatoic acid (acid). A value of 290 mgKOH / g) was obtained.
実施例1
撹拌装置、冷却管、温度計及び窒素導入管を備えた反応容器に、インドネシア産のガムロジン(ジヒドロアガト酸10重量%、アビエチン酸35重量%、デヒドロアビエチン酸5重量%、酸価190mgKOH/g、軟化点80℃。以下、IDロジンともいう。)50部と中国産のガムロジン(ジヒドロアガト酸0重量%、アビエチン酸50重量%、デヒドロアビエチン酸5重量%、酸価170mgKOH/g、軟化点75℃。以下、CNロジンともいう。)50部とを仕込み、200℃で溶融させた。次いで、反応系にフマル酸1部を仕込み、200℃で1時間反応させた。次いで、同温度の溶融物に、ペンタエリスリトール15部を仕込み、窒素ガス気流下、280℃で10時間エステル化反応を行った。その後、3時間減圧処理することにより、強化ロジンエステルを合成した。物性を表1に示す。
Example 1
In a reaction vessel equipped with a stirrer, cooling tube, thermometer and nitrogen introduction tube, Indonesian gumrosin (dihydroagatoic acid 10% by weight, abietic acid 35% by weight, dehydroabietic acid 5% by weight, acid value 190 mgKOH / g, Softening point 80 ° C., hereinafter also referred to as ID rosin) 50 parts and Chinese gum rosin (dihydroagatoic acid 0% by weight, abietic acid 50% by weight, dehydroabietic acid 5% by weight, acid value 170 mgKOH / g, softening point 75) ° C. (hereinafter, also referred to as CN rosin) 50 parts were charged and melted at 200 ° C. Next, 1 part of fumaric acid was charged into the reaction system, and the reaction was carried out at 200 ° C. for 1 hour. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, and an esterification reaction was carried out at 280 ° C. for 10 hours under a nitrogen gas stream. Then, it was subjected to the reduced pressure treatment for 3 hours to synthesize a fortified rosin ester. The physical characteristics are shown in Table 1.
実施例2
実施例1と同様の反応容器に、IDロジン100部を仕込み、200℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール15部を仕込み、窒素ガス気流下280℃で10時間、エステル化反応を行い、次いで3時間減圧処理することによりロジンエステルを合成した。物性を表1に示す。
Example 2
In the same reaction vessel as in Example 1, 100 parts of ID rosin was charged and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, an esterification reaction was carried out at 280 ° C. under a nitrogen gas stream for 10 hours, and then a reduced pressure treatment was carried out for 3 hours to synthesize a rosin ester. The physical characteristics are shown in Table 1.
実施例3
実施例1と同様の反応容器に、CNロジン70部とIDロジン30部とを仕込み、200℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール15部を仕込み、窒素ガス気流下に280℃で10時間、エステル化反応を行い、次いで3時間減圧処理することにより、ロジンエステルを合成した。物性を表1に示す。
Example 3
In the same reaction vessel as in Example 1, 70 parts of CN rosin and 30 parts of ID rosin were charged and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, an esterification reaction was carried out at 280 ° C. for 10 hours under a nitrogen gas stream, and then a reduced pressure treatment was carried out for 3 hours to synthesize a rosin ester. The physical characteristics are shown in Table 1.
実施例4
実施例1と同様の反応容器に、IDロジン98部と製造例1で得られた樹脂酸組成物 2部とを仕込み、200℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール14部を仕込み、窒素ガス気流下に280℃で12時間、エステル化反応を行い、次いで5時間減圧処理することにより、ロジンエステルを合成した。物性を表1に示す。
Example 4
In the same reaction vessel as in Example 1, 98 parts of ID rosin and 2 parts of the resin acid composition obtained in Production Example 1 were charged and melted at 200 ° C. Next, 14 parts of pentaerythritol was charged into the melt at the same temperature, an esterification reaction was carried out at 280 ° C. for 12 hours under a nitrogen gas stream, and then a reduced pressure treatment was carried out for 5 hours to synthesize a rosin ester. The physical characteristics are shown in Table 1.
比較例1
実施例1と同様の反応容器に、CNロジン100部を仕込み、窒素ガス気流下200℃で溶融させた。次いで、反応系にフマル酸1部を仕込み、200℃で1時間反応させた。次いで、同温度の溶融物に、ペンタエリスリトール15部を仕込み、窒素ガス気流下で280℃で10時間、エステル化反応を行った。その後、3時間減圧処理することにより、強化ロジンエステルを合成した。物性を表1に示す。
Comparative Example 1
In the same reaction vessel as in Example 1, 100 parts of CN rosin was charged and melted at 200 ° C. under a nitrogen gas stream. Next, 1 part of fumaric acid was charged into the reaction system, and the reaction was carried out at 200 ° C. for 1 hour. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, and an esterification reaction was carried out at 280 ° C. for 10 hours under a nitrogen gas stream. Then, it was subjected to the reduced pressure treatment for 3 hours to synthesize a fortified rosin ester. The physical characteristics are shown in Table 1.
比較例2
実施例1と同様の反応容器に、CNロジン100部を溶融し、フマル酸5部を仕込み、200℃で1時間反応させる。次いでペンタエリスリトール13部を仕込み、窒素ガス気流下280℃まで昇温し同温度で10時間、エステル化反応を行った。その後、3時間減圧処理することにより、強化ロジンエステルを合成した。物性を表1に示す。
Comparative Example 2
In the same reaction vessel as in Example 1, 100 parts of CN rosin is melted, 5 parts of fumaric acid is charged, and the reaction is carried out at 200 ° C. for 1 hour. Next, 13 parts of pentaerythritol was charged, the temperature was raised to 280 ° C. under a nitrogen gas stream, and the esterification reaction was carried out at the same temperature for 10 hours. Then, it was subjected to the reduced pressure treatment for 3 hours to synthesize a fortified rosin ester. The physical characteristics are shown in Table 1.
比較例3
実施例1と同様の反応容器に、CNロジン100部を溶融し、200℃で溶融させた。次いで、同温度の溶融物に、ペンタエリスリトール15部を仕込み、窒素ガス気流下280℃で10時間、エステル化反応を行い、次いで3時間減圧処理することによりロジンエステルを合成した。物性を表1に示す。
Comparative Example 3
100 parts of CN rosin was melted in the same reaction vessel as in Example 1 and melted at 200 ° C. Next, 15 parts of pentaerythritol was charged into the melt at the same temperature, an esterification reaction was carried out at 280 ° C. under a nitrogen gas stream for 10 hours, and then a reduced pressure treatment was carried out for 3 hours to synthesize a rosin ester. The physical characteristics are shown in Table 1.
表1中、DHAAはジヒドロアガト酸を、AAはアビエチン酸、DAAはデヒドロアビエチン酸を意味する。
In Table 1, DHAA means dihydroagatoic acid, AA means abietic acid, and DAA means dehydroabietic acid.
2.ホットメルト接着剤の調製2. 2. Preparation of hot melt adhesive
実施例1の(A1)成分と、市販のエチレンー酢酸ビニル共重合体(商品名EVA#220、三井・デュポンポリケミカル(株)製)と、マイクロクリスタリンワックス(商品名Hi-Mic-1080、日本精鑞(株)製)部とを、重量比が4/4/2となるように混合し、加熱下に溶融させることによって、ホットメルト接着剤を調製した。 The component (A1) of Example 1, a commercially available ethylene-vinyl acetate copolymer (trade name EVA # 220, manufactured by Mitsui-Dupont Polychemical Co., Ltd.), and microcrystalline wax (trade name Hi-Mic-1080, Japan). A hot melt adhesive was prepared by mixing the parts (manufactured by Seikan Co., Ltd.) so that the weight ratio was 4/4/2 and melting them under heating.
<加熱安定性試験>
前記ホットメルト接着剤を25g秤量し、これを180℃の順風乾燥機内で加熱した際の濁り及び皮張りの有無を、24時間目、48時間目及び72時間目のそれぞれにおいて、以下の基準で目視確認した。結果を表2に示す。
○:濁り、皮張りなし
△:濁り、皮張りがやや生じている
×:濁り、皮張りが強く生じている
<Heating stability test>
Weighing 25 g of the hot melt adhesive and heating it in a smooth air dryer at 180 ° C., the presence or absence of turbidity and skinning was determined according to the following criteria at the 24th, 48th, and 72nd hours, respectively. It was visually confirmed. The results are shown in Table 2.
○: Turbidity, no skinning △: Turbidity, some skinning ×: Turbidity, strong skinning
<溶融粘度の測定>
前記ホットメルト接着剤の150℃及び180℃のそれぞれにおける粘度を、市販のB型粘度計(ローター:HM-3、回転速度:3rpm)で測定した。結果を表2に示す。
<Measurement of melt viscosity>
The viscosities of the hot melt adhesive at 150 ° C. and 180 ° C. were measured with a commercially available B-type viscometer (rotor: HM-3, rotation speed: 3 rpm). The results are shown in Table 2.
<相溶性>
実施例1の(A1)成分2gと、EVA#220 2gと試験管に入れ、加熱下に混合し、溶融させた後、該溶融物を更に200℃に達するまで加熱してから放冷し、外観に濁りが生じた温度(曇点)を測定した。他の実施例及び比較例のロジンエステルについても同様にして混合物を調製し、その曇点を同様に測定した。結果を表2に示す。
<Compatibility>
2 g of the component (A1) of Example 1 and EVA # 220 2 g were placed in a test tube, mixed under heating and melted, and then the melt was further heated to 200 ° C. and then allowed to cool. The temperature at which the appearance became turbid (cloud point) was measured. Mixtures were prepared in the same manner for the rosin esters of the other examples and comparative examples, and the cloud point was measured in the same manner. The results are shown in Table 2.
<耐熱保持力>
実施例1に係るホットメルト接着剤をアルミ基材に塗工し、縦7.5cm、横2.5
cm幅に切断。これを別のアルミ被着体に圧着させた後、23℃で1日放置した。次いで、市販のクリープ測定装置(製品名:恒温恒湿槽付保持力試験機、テスター産業(株)製)を用い、荷重1kg、温度60℃の条件で、当該荷重物品が落下するまでの時間を測定し、下記基準で耐熱保持力を評価した。
○:2時間以上
△:1.5時間以上2時間未満
×:1.5時間未満
<Heat resistance holding power>
The hot melt adhesive according to Example 1 was applied to an aluminum base material, and the length was 7.5 cm and the width was 2.5.
Cut to cm width. This was crimped to another aluminum adherend and then left at 23 ° C. for 1 day. Next, using a commercially available creep measuring device (product name: holding force tester with constant temperature and humidity chamber, manufactured by Tester Sangyo Co., Ltd.), the time until the loaded article falls under the conditions of a load of 1 kg and a temperature of 60 ° C. Was measured, and the heat-resistant holding power was evaluated according to the following criteria.
◯: 2 hours or more Δ: 1.5 hours or more and less than 2 hours ×: less than 1.5 hours
Claims (4)
前記ロジン類(a1)における二塩基性ジテルペンカルボン酸、アビエチン酸及びデヒドロアビエチン酸の含有量が、順に3~13重量%、20重量%以上60重量%未満及び5重量%以上30重量%未満である粘着付与樹脂。
The contents of the diterpene carboxylic acid, abietic acid and dehydroabietic acid in the rosins (a1) are 3 to 13 % by weight, 20% by weight or more and less than 60% by weight, and 5% by weight or less and less than 30% by weight, respectively. A certain adhesive resin.
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WO2017065072A1 (en) | 2015-10-15 | 2017-04-20 | ハリマ化成株式会社 | Tackifier |
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