JP6048801B2 - Polyamide polyamine condensate, polyamide polyamine crosslinkable modified product, curing agent for epoxy resin, cured epoxy resin, aqueous adhesive composition and wet paper strength agent - Google Patents

Polyamide polyamine condensate, polyamide polyamine crosslinkable modified product, curing agent for epoxy resin, cured epoxy resin, aqueous adhesive composition and wet paper strength agent Download PDF

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JP6048801B2
JP6048801B2 JP2012200307A JP2012200307A JP6048801B2 JP 6048801 B2 JP6048801 B2 JP 6048801B2 JP 2012200307 A JP2012200307 A JP 2012200307A JP 2012200307 A JP2012200307 A JP 2012200307A JP 6048801 B2 JP6048801 B2 JP 6048801B2
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田中 邦彦
邦彦 田中
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Arakawa Chemical Industries Ltd
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本発明は、環境配慮型でありしかも優れた諸特性を有する、重合ロジン系ポリアミドポリアミン縮合物およびその架橋性誘導体、ならびにそれらの用途に関する。 The present invention relates to a polymerized rosin-based polyamide polyamine condensate, a crosslinkable derivative thereof, and uses thereof, which are environmentally friendly and have various characteristics.

ポリアミドポリアミン縮合物は、エポキシ樹脂用硬化剤として用いられることが知られており、また該硬化剤とエポキシ樹脂からなる組成物や硬化物が、例えば塗料、接着剤などの各種用途に適用できることも知られている(例えば、特許文献1)。 Polyamide polyamine condensates are known to be used as curing agents for epoxy resins, and compositions and cured products comprising the curing agents and epoxy resins can be applied to various applications such as paints and adhesives. Known (for example, Patent Document 1).

また、ポリアミドポリアミン縮合物とエピハロヒドリンとの反応生成物である架橋性変性物は、例えば水性接着剤の配合成分として使用され(例えば、特許文献2)、また湿潤時の紙製品の強度を向上させるための湿潤紙力剤などの用途で賞用されている(例えば、特許文献3〜5)。 Further, a crosslinkable modified product, which is a reaction product of a polyamide polyamine condensate and an epihalohydrin, is used, for example, as a component of an aqueous adhesive (for example, Patent Document 2), and improves the strength of paper products when wet. Have been used in applications such as wet paper strength agents (for example, Patent Documents 3 to 5).

近年、環境保護・環境配慮の要請から、バイオマス利用による新規なバイオベースプラスチックの合成技術や、天然素材に着目したグリーン化技術などの開発努力が、多方面でなされている。   In recent years, in response to requests for environmental protection and environmental considerations, development efforts have been made in various fields, such as synthesis technology for new bio-based plastics using biomass and greening technology focusing on natural materials.

しかしながら、天然素材を単純に配合した組成物では、強度や耐水性などの性能が一般的に低下する傾向がある。そのため、天然素材を配合成分ではなく反応成分として導入することが望ましい。ところで、天然素材として脂肪酸やロジンがあげられるが、これらはいずれも一官能のカルボン酸であるため、各種プラスチックや樹脂の側鎖や末端部として導入できるものの、主鎖中に導入することは容易でなかった。そのため、例えば、ロジンを不飽和脂肪酸で変性したり、重合または二量化することにより多官能化合物に誘導して、これらを主鎖に組み入れる試みもなされている。しかしながら、該重合体や二量化物の純度が低いために、得られる目的物が所望の性能を発揮できないなどの課題がある。   However, a composition in which a natural material is simply blended generally tends to lower performance such as strength and water resistance. Therefore, it is desirable to introduce a natural material as a reaction component rather than a blending component. By the way, fatty acids and rosin are listed as natural materials. Since these are monofunctional carboxylic acids, they can be introduced as side chains and terminal parts of various plastics and resins, but are easy to introduce into the main chain. It was not. For this reason, for example, attempts have been made to incorporate rosin into a main chain by modifying it with an unsaturated fatty acid, polymerizing or dimerizing it into a polyfunctional compound. However, since the purity of the polymer or dimerized product is low, there is a problem that the obtained target product cannot exhibit desired performance.

そのため、斯界においては、従来の石油系素材から得られる用途物と比べて何ら遜色のない、天然系素材から得られる目的物の開発が切望されている。   Therefore, in this field, the development of a target product obtained from a natural material, which is inferior to a use product obtained from a conventional petroleum material, is eagerly desired.

特開平8−73570号公報([0030])JP-A-8-73570 ([0030]) 特開昭60−124675号公報JP-A-60-124675 特開平5−209159号公報([0008])JP-A-5-209159 ([0008]) 特開2005−208456号公報([0056])Japanese Patent Laying-Open No. 2005-208456 ([0056]) 特開平6−1842号公報([0002])Japanese Patent Laid-Open No. 6-1842 ([0002])

本発明は、環境配慮の観点から、天然素材である重合ロジン成分を含んでなるポリアミドポリアミン縮合物およびその架橋性変性物を提供し、各種用途にこれらを利用することを目的とする。 An object of the present invention is to provide a polyamide polyamine condensate comprising a polymerized rosin component, which is a natural material, and a crosslinkable modified product thereof from the viewpoint of environmental considerations, and an object thereof is to utilize them for various applications.

本発明者は前記従来技術の課題を解決すべく、重合ロジンまたはその低級エステルの使用量または純度と、目的物性能との相関に着目して、鋭意検討を重ねた。その結果、前記重合ロジン類を特定量以上含有してなるポリアミドポリアミン縮合物や該縮合物の架橋性変性物が前記課題を解決しうること、更には二量化物を特定量以上含有する重合ロジン類を用いてなるポリアミドポリアミン縮合物や該縮合物の架橋性変性物が、前記課題をより好適に解決しうることを見出し、本発明を完成するに至った。 In order to solve the above-mentioned problems of the prior art, the present inventor has intensively studied paying attention to the correlation between the amount or purity of the polymerized rosin or its lower ester and the performance of the target product. As a result, a polyamide polyamine condensate containing a specific amount or more of the polymerized rosin or a crosslinkable modified product of the condensate can solve the above problems, and further a polymerized rosin containing a specific amount or more of a dimerization product The present inventors have found that a polyamide polyamine condensate using a polymer and a crosslinkable modified product of the condensate can solve the above problems more suitably, and have completed the present invention.

すなわち本発明は、ジカルボン酸成分およびポリアルキレンポリアミン成分を縮合させてなるポリアミドポリアミン縮合物であって、該ジカルボン酸成分中に重合ロジンおよび/または重合ロジン低級エステルを20モル%以上含有するものであることを特徴とするポリアミドポリアミン縮合物(A)に係る。また本発明は、前記ポリアミドポリアミン(A)とエピハロヒドリンとを反応させて得られるポリアミドポリアミン架橋性変性物(B)に係る。また本発明は、ポリアミドポリアミン縮合物(A)を含んでなるエポキシ樹脂用硬化剤に係る。また本発明は、前記エポキシ樹脂用硬化剤を用いてエポキシ樹脂を硬化させて得られるエポキシ樹脂硬化物に係る。更に本発明は、ポリアミドポリアミン架橋性誘導体(B)を含んでなる水性接着剤組成物および湿潤紙力剤に係る。 That is, the present invention is a polyamide polyamine condensate obtained by condensing a dicarboxylic acid component and a polyalkylene polyamine component, and contains 20 mol% or more of polymerized rosin and / or polymerized rosin lower ester in the dicarboxylic acid component. The present invention relates to a polyamide polyamine condensate (A) characterized by being. The present invention also relates to a polyamide polyamine crosslinkable modified product (B) obtained by reacting the polyamide polyamine (A) with epihalohydrin. Moreover, this invention concerns on the hardening | curing agent for epoxy resins which comprises a polyamide polyamine condensate (A). Moreover, this invention relates to the epoxy resin hardened | cured material obtained by hardening an epoxy resin using the said hardening | curing agent for epoxy resins. The present invention further relates to an aqueous adhesive composition and a wet paper strength agent comprising the polyamide polyamine crosslinkable derivative (B).

本発明により、環境配慮型であり、しかも諸特性に優れたポリアミドポリアミン縮合物(A)およびポリアミドポリアミン架橋性誘導体(B)を提供できる。本発明で得られるポリアミドポリアミン縮合物(A)は、各種用途、例えばエポキシ樹脂用硬化剤として、エポキシ樹脂硬化物(塗料、接着剤など)用に使用できる。また本発明のポリアミドポリアミン架橋性変性物(B)は、例えば、水性接着剤組成物、湿潤紙力剤などに好適である。しかも本発明の縮合物(A)、架橋性変性物(B)を用いてなる用途物はいずれも、従来の石油系各用途物に比べて性能面で遜色がなく、環境保護などの目的にも資するものである。 According to the present invention, a polyamide polyamine condensate (A) and a polyamide polyamine crosslinkable derivative (B) which are environmentally friendly and excellent in various properties can be provided. The polyamide polyamine condensate (A) obtained in the present invention can be used for various uses, for example, for epoxy resin cured products (paints, adhesives, etc.) as a curing agent for epoxy resins. The polyamide polyamine crosslinkable modified product (B) of the present invention is suitable for, for example, an aqueous adhesive composition, a wet paper strength agent, and the like. In addition, the applications using the condensate (A) and the crosslinkable modified product (B) of the present invention are not inferior in terms of performance compared to conventional petroleum-based applications, and for purposes such as environmental protection. It also contributes.

本発明のポリアミドポリアミン縮合物(A)(以下、縮合物(A)という)は、後述のような二塩基酸および/またはその誘導体(以下、ジカルボン酸成分という)とポリアルキレンポリアミン(以下、ポリアミン成分という)との脱水縮合物であって、該ジカルボン酸成分中に重合ロジンおよび/または重合ロジン低級エステル(以下、重合ロジン類という)をそれらの合計で20モル%以上含有するもの、好ましくは40モル%以上含有するものである。なお、重合ロジン低級エステルにおける「低級」とは、メチル、エチル、プロピル基を意味する。 The polyamide polyamine condensate (A) of the present invention (hereinafter referred to as condensate (A)) is composed of a dibasic acid and / or a derivative thereof (hereinafter referred to as dicarboxylic acid component) and a polyalkylene polyamine (hereinafter referred to as polyamine). Component)) containing a polymerized rosin and / or polymerized rosin lower ester (hereinafter referred to as polymerized rosin) in a total of 20 mol% or more in the dicarboxylic acid component, preferably It contains 40 mol% or more. In the polymerized rosin lower ester, “lower” means a methyl, ethyl, or propyl group.

本発明で用いる重合ロジン類としては、特に限定はされないが、二量化物(二量化ロジン、二量化ロジン低級エステル)の含有率が40重量%以上、好ましくは50重量%以上、より好ましくは80重量%以上であるものを用いるのがよい。目的用途において、色調が重視される場合には、該重合ロジン類としては、蒸留ロジンを出発原料とする重合ロジン類や、該水素化物などを使用することがより好ましい。前記の重合ロジン類の製造法としては、特に限定されず、公知各種の方法を採用できる。 The polymerized rosins used in the present invention are not particularly limited, but the content of the dimerized product (dimerized rosin, dimerized rosin lower ester) is 40% by weight or more, preferably 50% by weight or more, more preferably 80%. It is good to use what is weight% or more. When the color tone is important in the intended use, it is more preferable to use polymerized rosins starting from distilled rosin, hydrides, etc. as the polymerized rosins. It does not specifically limit as a manufacturing method of the said polymerized rosins, A well-known various method is employable.

前記二塩基酸としては、本発明での特徴部分となる重合ロジンの他、例えばマロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸などの脂肪族二塩基酸;フタル酸、イソフタル酸、テレフタル酸などの芳香族二塩基酸などがあげられる。該二塩基酸の誘導体としては、本発明での特徴部分となる重合ロジン低級エステルの他、前記二塩基酸の無水物や低級エステルなどがあげられる。これらジカルボン酸成分としては、重合ロジン類を前記のように特定量以上使用することが必要であるが、他のジカルボン酸成分については、任意使用でき、いずれか1種単独でまたは適宜に組み合わせて用いられる。 As the dibasic acid, in addition to polymerized rosin, which is a characteristic part of the present invention, for example, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Acids: aromatic dibasic acids such as phthalic acid, isophthalic acid and terephthalic acid. Examples of the dibasic acid derivative include the polymerized rosin lower ester, which is a characteristic part of the present invention, and the dibasic acid anhydride and lower ester. As these dicarboxylic acid components, it is necessary to use polymerized rosins in a specific amount or more as described above, but other dicarboxylic acid components can be used arbitrarily, and any one of them can be used alone or in combination as appropriate. Used.

縮合物(A)に用いられる前記ポリアミン成分としては、例えば、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、イミノビスプロピルアミンなどがあげられる。これらポリアミン成分は1種単独でまたは適宜に組み合わせて使用できる。 Examples of the polyamine component used in the condensate (A) include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and iminobispropylamine. These polyamine components can be used alone or in appropriate combination.

縮合物(A)は、前記ジカルボン酸成分とポリアミン成分とを、公知の方法で脱水縮合や脱アルコール縮合させることにより容易に製造できる。例えば、硫酸、ベンゼンスルホン酸、パラトルエンスルホン酸などの触媒の存在下または不存在下に、反応温度110〜250℃程度で、2〜24時間程度の条件で反応させればよい。ジカルボン酸成分とポリアミン成分の使用割合は、格別限定されないが、通常は前者:後者が1:0.9〜1.2程度(モル比)の範囲で使用するのが好ましい。 The condensate (A) can be easily produced by subjecting the dicarboxylic acid component and the polyamine component to dehydration condensation or dealcoholization condensation by a known method. For example, the reaction may be carried out in the presence or absence of a catalyst such as sulfuric acid, benzenesulfonic acid, paratoluenesulfonic acid and the like at a reaction temperature of about 110 to 250 ° C. for about 2 to 24 hours. The use ratio of the dicarboxylic acid component and the polyamine component is not particularly limited, but it is usually preferable that the former: the latter is used in the range of about 1: 0.9 to 1.2 (molar ratio).

縮合物(A)の性状や一般恒数については、特に限定はされず、その用途に応じて適宜に設定すればよい。縮合物(A)の重量平均分子量は、通常は1000〜3000程度、好ましくは1200〜2500である。縮合物(A)のアミン価は、固形分換算で10〜50mgKOH/g程度、好ましくは20〜40mgKOH/gである。該アミン価が前記下限値より過小であればエポキシ樹脂の硬化性が低下する傾向があり、また該アミン価が前記上限値より過大であれば、得られるエポキシ硬化物の接着強度が低下する傾向がある。なお、縮合物(A)は、後述のポリアミドポリアミン架橋性変性物(B)の製造におけるエピハロヒドリンとの反応にあたっては、水性液の形態であることが好ましく、該水性液とは水溶液または水分散液をいう。また、該水性液に用いる溶媒としては、水の他、例えばエチルアルコール、イソプロピルアルコールなどの低級アルコールが挙げられる。 The properties and general constants of the condensate (A) are not particularly limited, and may be appropriately set depending on the application. The weight average molecular weight of the condensate (A) is usually about 1000 to 3000, preferably 1200 to 2500. The amine value of the condensate (A) is about 10 to 50 mgKOH / g, preferably 20 to 40 mgKOH / g in terms of solid content. If the amine value is less than the lower limit value, the curability of the epoxy resin tends to decrease. If the amine value is greater than the upper limit value, the adhesive strength of the resulting epoxy cured product tends to decrease. There is. The condensate (A) is preferably in the form of an aqueous liquid in the reaction with the epihalohydrin in the production of the polyamide polyamine crosslinkable modified product (B) described later. The aqueous liquid is an aqueous solution or an aqueous dispersion. Say. In addition to water, examples of the solvent used in the aqueous liquid include lower alcohols such as ethyl alcohol and isopropyl alcohol.

本発明のポリアミドポリアミン架橋性変性物(B)(以下、変性物(B)という)は、前記縮合物(A)とエピハロヒドリンとを反応させて得られる。エピハロヒドリンとしては、例えばエピクロロヒドリン、エピブロムヒドリンなどが用いられる。縮合物(A)に対するエピハロヒドリンの使用割合は、特に限定されないが、低分子有機ハロゲン化合物の生成量を低減させるなどの観点から、通常、縮合物(A)の第2級アミノ基とエピハロヒドリンのエポキシ基の当量比(エポキシ基/第2級アミノ基)が0.8〜2.0の範囲内となるように用いるのが好ましい。低分子有機ハロゲン化合物の生成量を低減させるには、前記当量比は1.5以下とするのがより好ましく、また得られる変性物(B)の水性液としての保存安定性や、目的物の諸性能(接着性、耐水化効果、湿潤紙力効果など)を考慮すれば、前記当量比は0.9以上とするのがより好ましい。 The polyamide polyamine crosslinkable modified product (B) of the present invention (hereinafter referred to as modified product (B)) is obtained by reacting the condensate (A) with epihalohydrin. As the epihalohydrin, for example, epichlorohydrin, epibromohydrin, or the like is used. The ratio of the epihalohydrin to the condensate (A) is not particularly limited, but from the viewpoint of reducing the amount of low-molecular organic halogen compound produced, the secondary amino group of the condensate (A) and the epoxy of epihalohydrin are usually used. It is preferably used so that the equivalent ratio of groups (epoxy group / secondary amino group) is in the range of 0.8 to 2.0. In order to reduce the amount of low-molecular organic halogen compound produced, the equivalent ratio is more preferably 1.5 or less, and the storage stability of the resulting modified product (B) as an aqueous liquid, Considering various performances (adhesiveness, water resistance effect, wet paper strength effect, etc.), the equivalent ratio is more preferably 0.9 or more.

変性物(B)の性状や一般恒数については、特に限定はされず、その用途に応じて適宜に設定すればよい。変性物(B)を、例えば水性接着剤や湿潤紙力剤に用いる場合には、該分子量は格別限定されないが、25℃における50重量%水性液の粘度が100〜1000mPa・s程度のものが、取り扱い性や性能面で好ましい。 The properties and general constants of the modified product (B) are not particularly limited, and may be appropriately set according to the application. When the modified product (B) is used in, for example, an aqueous adhesive or a wet paper strength agent, the molecular weight is not particularly limited, but the viscosity of a 50 wt% aqueous liquid at 25 ° C. is about 100 to 1000 mPa · s. It is preferable in terms of handleability and performance.

縮合物(A)とエピハロヒドリンとの反応は、縮合物(A)にエピハロヒドリンを付加させる工程と、更に架橋により増粘させる工程を含む。かかる反応温度は、通常、5〜80℃程度が好ましく、反応液は通常、20〜70重量%程度とするのが好ましい。かかる反応条件は適宜に調整できるが、低分子有機ハロゲン化合物の生成を抑え易く、また反応の制御が容易なことから、反応温度は、縮合物(A)にエピハロヒドリンを付加させる温度(5〜40℃:1次保温)と、更に増粘させる温度(40〜80℃:2次保温)の2段階に設定して行なうのが好ましい。反応温度を2段階に設定する場合、反応液濃度は、前記1次保温の濃度に比べて2次保温の濃度が同等またはそれ以下となるようにするのが好ましい。反応液の濃度は、たとえば、1次保温では30〜70重量%程度、2次保温では20〜40重量%程度に調整するのが好ましい。 The reaction of the condensate (A) with epihalohydrin includes a step of adding epihalohydrin to the condensate (A) and a step of further thickening by crosslinking. The reaction temperature is usually preferably about 5 to 80 ° C., and the reaction solution is usually preferably about 20 to 70% by weight. Although such reaction conditions can be adjusted as appropriate, the reaction temperature is a temperature at which epihalohydrin is added to the condensate (A) (5 to 40) because it is easy to suppress the formation of low molecular weight organic halogen compounds and the control of the reaction is easy. It is preferable to carry out by setting in two stages, namely, (C: primary heat retention) and a temperature for further thickening (40-80 ° C .: secondary heat retention). When the reaction temperature is set in two stages, it is preferable that the concentration of the reaction solution is equal to or lower than the concentration of the secondary temperature compared to the concentration of the primary temperature. The concentration of the reaction solution is preferably adjusted to, for example, about 30 to 70% by weight for the primary heat retention and about 20 to 40% by weight for the second heat retention.

本発明の縮合物(A)は、エポキシ樹脂用硬化剤として好適である。適用されるエポキシ樹脂については格別限定されず、各種公知のものが使用できる。例えば、ノボラック型エポキシ樹脂、トリスフェノールエポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、脂環式エポキシ樹脂などがあげられ、これらは単独で用いてもよく、2種以上併用してもよい。エポキシ樹脂に対する該硬化剤の配合割合は、格別限定されないが、通常は固形分換算で、エポキシ樹脂100重量部に対し該硬化剤は10〜150重量部程度、好ましくは20〜100重量部とされる。別言すると、該硬化剤の使用量は、エポキシ樹脂のエポキシ基1当量に対して硬化剤の残存アミノ基として0.5〜1.5当量が好ましく、特に0.7〜1.2当量が好ましい。 The condensate (A) of the present invention is suitable as a curing agent for epoxy resins. The applied epoxy resin is not particularly limited, and various known ones can be used. For example, novolac type epoxy resin, trisphenol epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, etc. are used alone. It may be used in combination of two or more. The blending ratio of the curing agent with respect to the epoxy resin is not particularly limited, but is usually about 10 to 150 parts by weight, preferably 20 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin in terms of solid content. The In other words, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.7 to 1.2 equivalents as the residual amino group of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin. preferable.

また前記のエポキシ樹脂組成物の調製に際して、必要に応じて、各種公知の硬化促進剤を使用してもよい。例えば、2−メチルイミダゾール、2−エチルイミダゾールなどのイミダゾール系化合物、2−(ジメチルアミノメチル)フェノールなどの第3級アミン系化合物、トリフェニルフォスフィン化合物などが使用できる。これらは単独で用いてもよく、2種以上を併用してもよい。硬化促進剤を用いる場合、その使用量はエポキシ樹脂100重量部に対して0.01〜15重量部の範囲が好ましく、特に0.1〜10重量部の範囲が好ましい。また、当該調製に際しては、必要に応じて各種公知の有機溶剤を用いて、エポキシ樹脂組成物の粘度を適宜に調整することができる。 Moreover, when preparing the said epoxy resin composition, you may use various well-known hardening accelerators as needed. For example, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, and triphenylphosphine compounds can be used. These may be used alone or in combination of two or more. When a curing accelerator is used, the amount used is preferably in the range of 0.01 to 15 parts by weight, particularly preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. Moreover, in the said preparation, the viscosity of an epoxy resin composition can be suitably adjusted using various well-known organic solvents as needed.

本発明の縮合物(A)は、例えば脂肪酸ダイマー系ポリアミドポリアミン縮合物などに比べて、耐熱性に優れたエポキシ樹脂硬化物を提供できる。縮合物(A)に見られる該効果の発現理由は定でないが、ジカルボン酸成分として構造的にバルキーな重合ロジン類が特定量以上使用されていることが一因であると思われる。 The condensate (A) of the present invention can provide an epoxy resin cured product having excellent heat resistance as compared with, for example, a fatty acid dimer-based polyamide polyamine condensate. The reason for the manifestation of the effect seen in the condensate (A) is not clear, but it seems to be due to the use of a structurally bulky polymerized rosin as a dicarboxylic acid component in a specific amount or more.

本発明の変性物(B)は、各種の水性接着剤組成物における配合成分として好適に使用できる。具体的には、澱粉系水性接着剤に添加される耐水化剤、水溶性エポキシ化合物に適用可能な硬化剤、合成樹脂エマルジョンなどと併用可能な耐水化剤、偏光板用の接着剤成分などがあげられるが、これらに限定されるものではない。水性接着剤組成物における変性物(B)の使用量は、一概に限定できないが、例えば、澱粉系水性接着剤用の耐水化剤として用いる場合は、通常、澱粉100重量部に対して0.1〜15重量部(固形分換算)程度であり、好ましくは1〜10重量部の割合で配合される。また、合成樹脂エマルジョンなどと併用可能な耐水化剤として用いる場合は、通常、合成樹脂エマルジョンの固形分100重量部に対して0.1〜30重量部(固形分換算)程度であり、好ましくは1〜20重量部の割合で配合される。 The modified product (B) of the present invention can be suitably used as a blending component in various aqueous adhesive compositions. Specifically, water-resistant agents added to starch-based aqueous adhesives, curing agents applicable to water-soluble epoxy compounds, water-resistant agents that can be used in combination with synthetic resin emulsions, adhesive components for polarizing plates, etc. However, it is not limited to these. Although the usage-amount of the modified | denatured material (B) in an aqueous adhesive composition cannot be generally limited, for example, when using as a water-proofing agent for starch-type aqueous adhesives, it is usually 0.00 with respect to 100 weight part of starch. It is about 1 to 15 parts by weight (in terms of solid content), preferably 1 to 10 parts by weight. In addition, when used as a water-proofing agent that can be used in combination with a synthetic resin emulsion or the like, it is usually about 0.1 to 30 parts by weight (in terms of solid content) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion, preferably It mix | blends in the ratio of 1-20 weight part.

また本発明の変性物(B)は、湿潤紙力剤として好適であり、例えばパルプ繊維の抄造のみならず、該繊維と鉱物繊維(石綿、岩綿など)や合成繊維(ポリアミド、ポリエステル、ポリオレフィンなど)とを混抄することにより、紙、板紙、繊維板などの製造に際して有利に適用できる。変性物(B)の使用量は、公知の湿潤紙力剤と同様、紙の用途により必要な物性が異なるため、用途に応じて適宜決定する必要があるが、通常、パルプ100重量部に対し、0.05〜1.0重量部程度が適当である。 The modified product (B) of the present invention is suitable as a wet paper strength agent. For example, not only pulp fiber papermaking but also fibers and mineral fibers (asbestos, rock wool, etc.) and synthetic fibers (polyamide, polyester, polyolefin) Etc.) can be advantageously applied in the production of paper, paperboard, fiberboard and the like. The amount of the modified product (B) used, as in the case of known wet paper strength agents, varies depending on the use of the paper, so it is necessary to determine it appropriately according to the use. 0.05 to 1.0 part by weight is appropriate.

以下に実施例および比較例をあげて本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。尚、部および%は特記しない限り重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

実施例1(ポリアミドポリアミン縮合物(A)の合成)
温度計、冷却器、攪拌機および窒素導入管を備えた反応装置に、重合ロジン(二量体含有率:40%)420部(1モル)、アジピン酸584部(4モル)およびジエチレントリアミン516部(5モル)を仕込み、窒素気流下180℃まで昇温し、生成水を系外に除去しながら約8時間を要して縮合反応させて、重量平均分子量が1600のポリアミドポリアミン縮合物を得た(A−1という)。次いで、所定量の水で希釈し、固形分濃度50%、粘度300mPa・s(25℃)のポリアミドポリアミン縮合物水溶液を得た(A−1’という)。
Example 1 (Synthesis of polyamide polyamine condensate (A))
In a reactor equipped with a thermometer, a condenser, a stirrer and a nitrogen introduction tube, 420 parts (1 mole) of polymerized rosin (dimer content: 40%), 584 parts (4 moles) of adipic acid and 516 parts of diethylenetriamine ( 5 moles), the temperature was raised to 180 ° C. under a nitrogen stream, and the condensation reaction took about 8 hours while removing the generated water out of the system to obtain a polyamide polyamine condensate having a weight average molecular weight of 1600. (Referred to as A-1). Then, it was diluted with a predetermined amount of water to obtain a polyamide polyamine condensate aqueous solution having a solid content of 50% and a viscosity of 300 mPa · s (25 ° C.) (referred to as A-1 ′).

実施例2〜4(ポリアミドポリアミン縮合物(A)の合成)
実施例1において、重合ロジンの種類、その使用割合のいずれかにつき、表1記載のように変更した他は、同様に縮合反応させて各種のポリアミドポリアミン縮合物(A)を得た(順にA−2〜A−4という)。次いで、これらを水で希釈し、各種の縮合物(A)水性液を得た(順に、A−2’〜A−4’という)。これらの重量平均分子量、粘度は表2に示す。
Examples 2 to 4 (Synthesis of polyamide polyamine condensate (A))
In Example 1, various polyamide polyamine condensates (A) were obtained in the same manner except that the type of polymerized rosin and the usage ratio thereof were changed as shown in Table 1 to obtain various polyamide polyamine condensates (A in order). -2 to A-4). Subsequently, these were diluted with water, and various condensate (A) aqueous liquids were obtained (in order, A-2 ′ to A-4 ′). These weight average molecular weights and viscosities are shown in Table 2.


表1中、重合ロジンNo.1とは実施例1で用いたもの、No.2とは二量化物の含有率が50%のもの、No.3とは二量化物の含有率が40%であって水素化されたものをいう。

In Table 1, the polymerized rosin No. 1 is the one used in Example 1, No. 2 is the dimerized product content of 50%, and No. 3 is the dimerized product content of 40%. It is hydrogenated.

比較例1(比較用ポリアミドポリアミン縮合物の合成)
実施例1で用いたと同様の反応装置に、アジピン酸730部(5モル)およびジエチレントリアミン516部(5モル)を仕込み、窒素気流下180℃まで昇温し、生成水を系外に除去しながら約8時間を要して縮合反応させて比較用ポリアミドポリアミン縮合物を得た(AC−1という)。次いで、所定量の水で希釈し、比較用ポリアミドポリアミン縮合物水性液を得た(AC−1’という)。これらの重量平均分子量、粘度は表2に示す。
Comparative Example 1 (Synthesis of polyamide polyamine condensate for comparison)
A reactor similar to that used in Example 1 was charged with 730 parts (5 moles) of adipic acid and 516 parts (5 moles) of diethylenetriamine, heated to 180 ° C. under a nitrogen stream, and the generated water was removed from the system. About 8 hours were required for the condensation reaction to obtain a comparative polyamide polyamine condensate (referred to as AC-1). Subsequently, it diluted with the predetermined amount of water, and obtained the polyamide polyamine condensate aqueous liquid for a comparison (it is called AC-1 '). These weight average molecular weights and viscosities are shown in Table 2.

比較例2(比較用ポリアミドポリアミン縮合物の合成)
実施例1で用いたと同様の反応装置に、脂肪酸ダイマー1122部(2モル)、アジピン酸438部(3モル)、およびジエチレントリアミン516部(5モル)を仕込み、窒素気流下180℃まで昇温し、生成水を系外に除去しながら約8時間を要して縮合反応させて比較用縮合物を得た(AC−2という)。次いで、所定量の水で希釈し、比較用ポリアミドポリアミン縮合物水性液を得た(AC−2’という)。これらの重量平均分子量、粘度は表2に示す。
Comparative Example 2 (Synthesis of polyamide polyamine condensate for comparison)
In a reactor similar to that used in Example 1, 1122 parts (2 moles) of fatty acid dimer, 438 parts (3 moles) of adipic acid, and 516 parts (5 moles) of diethylenetriamine were heated to 180 ° C. under a nitrogen stream. A condensation product for comparison was obtained by carrying out a condensation reaction taking about 8 hours while removing the produced water out of the system (referred to as AC-2). Subsequently, it diluted with the predetermined amount of water, and obtained the polyamide polyamine condensate aqueous liquid for a comparison (it is called AC-2 '). These weight average molecular weights and viscosities are shown in Table 2.

実施例5(ポリアミドポリアミン架橋性変性物(B)の合成)
実施例1で用いたと同様の反応装置に、実施例1で得られたA−1’を540部および水238部を仕込み(反応液濃度40%に調整)、系内温度を15℃に保持しながらエピクロロヒドリン92部(エピクロロヒドリンのエポキシ基:ポリアミドポリアミンの第2級アミノ基(当量比)=1.1:1)を2時間かけて滴下した後、30℃で5時間保温した。次いで、水90部を加えた後、60℃に昇温し2時間保温した。更に、水423部、62.5%硫酸50部を加えて冷却し、固形分濃度25%、粘度250mPa・s(25℃)、pH3.0のポリアミドポリアミン−エピクロロヒドリン樹脂水性液を得た(変性物B−1という)。
Example 5 (Synthesis of polyamide polyamine crosslinkable modified product (B))
540 parts of A-1 ′ obtained in Example 1 and 238 parts of water were prepared (adjusted to a reaction solution concentration of 40%) in the same reaction apparatus as used in Example 1, and the system temperature was maintained at 15 ° C. Then, 92 parts of epichlorohydrin (epoxy group of epichlorohydrin: secondary amino group of polyamidopolyamine (equivalent ratio) = 1.1: 1) was added dropwise over 2 hours, and then at 30 ° C. for 5 hours. Keep warm. Next, after adding 90 parts of water, the temperature was raised to 60 ° C. and kept for 2 hours. Further, 423 parts of water and 50 parts of 62.5% sulfuric acid were added and cooled to obtain a polyamide polyamine-epichlorohydrin resin aqueous solution having a solid content concentration of 25%, a viscosity of 250 mPa · s (25 ° C.), and a pH of 3.0. (Referred to as modified product B-1).

実施例6〜8
実施例5において、A−1’と該使用量を、表3に記載のように縮合物水性液の種類および使用量に変えた他は同様に反応を行い、ポリアミドポリアミン−エピクロロヒドリン変性物水溶液を得た(順に、変性物B−2〜B−4という)。これらの固形分濃度、粘度およびpHを表4に示す。
Examples 6-8
In Example 5, the reaction was carried out in the same manner except that the amount of A-1 ′ and the amount used was changed to the kind and amount of the condensate aqueous solution as shown in Table 3, and modified with polyamide polyamine-epichlorohydrin. A product aqueous solution was obtained (in order, modified products B-2 to B-4). Table 4 shows the solid content concentration, viscosity, and pH.

比較例3〜4
実施例5において、A−1’と該使用量に代えて、表3に記載のように変えた他は同様に反応を行い、比較用ポリアミドポリアミン−エピクロロヒドリン変性物水溶液を得た(順に、変性物BC−1およびBC−2という)。これらの固形分濃度、粘度およびpHを表4に示す。
Comparative Examples 3-4
In Example 5, the reaction was carried out in the same manner except that A-1 ′ and the amount used were changed as shown in Table 3 to obtain a comparative polyamide polyamine-epichlorohydrin modified aqueous solution ( In this order, they are referred to as modified products BC-1 and BC-2). Table 4 shows the solid content concentration, viscosity, and pH.

以下、本発明の縮合物および架橋性変性物を用いた特定用途における性能評価例を示す。 Hereinafter, performance evaluation examples in specific applications using the condensate and the crosslinkable modified product of the present invention will be shown.

(エポキシ樹脂接着剤組成物の調製)
実施例1〜4で得られた変性物(A−1〜A−4)および比較例1〜2で得られた比較用変性物(AC−1およびAC−2)について、ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン社製、商品名「EP828」)100部に対して、それぞれ50部および硬化促進剤(トリフェニルフォスフィン)1部を配合し、均一に混合し、硬化条件(150℃×2時間+180℃×8時間)でトランスファー成形して樹脂成形体を得た。これにより得られた硬化物のガラス転移温度(TMA 昇温度速度2℃/分)、熱変形温度(JIS K7207準拠)を測定した。結果を表5に示す。
(Preparation of epoxy resin adhesive composition)
Regarding the modified products (A-1 to A-4) obtained in Examples 1 to 4 and the modified products for comparison (AC-1 and AC-2) obtained in Comparative Examples 1 and 2, bisphenol A type epoxy resins (100 parts by Japan Epoxy Resin Co., Ltd., trade name “EP828”) 50 parts and 1 part of a curing accelerator (triphenylphosphine) are blended and mixed uniformly, and curing conditions (150 ° C. × 2 Time + 180 ° C. × 8 hours) to obtain a resin molded body. The glass transition temperature (TMA temperature increase rate 2 ° C./min) and heat distortion temperature (based on JIS K7207) of the cured product thus obtained were measured. The results are shown in Table 5.

表5から、各実施例の縮合物を用いてなるエポキシ樹脂硬化物は、比較用のエポキシ樹脂硬化物に比べてガラス転移温度、熱変形温度ともに高い値を示し、硬化物特性に優れることが明らかである。 From Table 5, the epoxy resin cured product using the condensate of each example shows higher values for both the glass transition temperature and the heat distortion temperature than the epoxy resin cured product for comparison, and is excellent in cured product characteristics. it is obvious.

(水性接着剤組成物の調製)
実施例5〜8で得られた変性物(B−1〜B−4)および比較例3〜4で得られた比較用変性物(BC−1およびBC−2)について、以下の方法で耐水接着剤を調製し、耐水化剤としての性能を評価した。結果を表6に示す。
(Preparation of aqueous adhesive composition)
The modified products (B-1 to B-4) obtained in Examples 5 to 8 and the modified products for comparison (BC-1 and BC-2) obtained in Comparative Examples 3 to 4 were water resistant by the following method. Adhesives were prepared and their performance as waterproofing agents were evaluated. The results are shown in Table 6.

40℃の温水585部にコーンスターチ240部を懸濁させ、ついで15%水酸化ナトリウム水溶液44.6部を添加し、その後硼酸3.2gを加えて糊液を得た。これに、スチレンブタジエンラテックス(固形分51%、Tg−5℃、平均粒子径130nm)150部、および耐水化剤として前記変性物24部を添加して、耐水接着剤を調製した。得られた接着剤を、坪量200g/m、撥水度(JIS P8137)R0の耐水中芯を貼合した片面段ボールの段頂に着糊量が固形分として10g/mになるように塗布し、これに耐水ライナーSKを貼り合わせて、熱圧着(160℃×5秒)した。貼合後の段ボールシートは温度23℃、湿度50%で24時間放置し、JIS−Z−0402に基づき常態接着力および耐水接着力(試験片を20℃の水に1時間浸漬後の接着力)を測定した。 240 parts of corn starch was suspended in 585 parts of warm water at 40 ° C., then 44.6 parts of a 15% aqueous sodium hydroxide solution was added, and then 3.2 g of boric acid was added to obtain a paste solution. To this, 150 parts of styrene butadiene latex (solid content 51%, Tg-5 ° C., average particle diameter 130 nm) and 24 parts of the modified product as a water-resistant agent were added to prepare a water-resistant adhesive. The obtained adhesive is 10 g / m 2 in terms of solid content on the top of a single-sided cardboard having a basis weight of 200 g / m 2 and a water-resistant core with a water repellency (JIS P8137) R0 bonded thereto. Then, a water-resistant liner SK was bonded thereto and thermocompression bonded (160 ° C. × 5 seconds). After bonding, the corrugated cardboard sheet is allowed to stand for 24 hours at a temperature of 23 ° C. and a humidity of 50%. Based on JIS-Z-0402, the normal state adhesive strength and water-resistant adhesive strength ) Was measured.

表6から、各実施例の変性物を用いてなる水性接着剤組成物は、比較用の水性接着剤組成物に比べて常態接着力、耐水接着力のいずれの点でも優れることが明らかであり、耐水化剤としての優位性が認められる。 From Table 6, it is clear that the aqueous adhesive composition using the modified product of each example is superior in both normal adhesive strength and water-resistant adhesive strength as compared with the comparative aqueous adhesive composition. The superiority as a waterproofing agent is recognized.

(湿潤紙力剤としての性能評価)
実施例5〜8で得られた変性物(B−1〜B−4)および比較例3〜4で得られた比較用変性物(BC−1およびBC−2)について、以下の方法で湿潤紙力剤としての性能を評価した。結果を表7に示す。
(Performance evaluation as wet paper strength agent)
The modified products (B-1 to B-4) obtained in Examples 5 to 8 and the modified products for comparison (BC-1 and BC-2) obtained in Comparative Examples 3 to 4 were wetted by the following method. The performance as a paper strength agent was evaluated. The results are shown in Table 7.

(湿潤紙力強度)
パルプ(L−BKP/N−BKP=1/1)を離解し、濾水量が500mlになるまで叩解したパルプスラリーに、前記の架橋反応物を0.4%(対パルプ固形分換算)加えた。こうして得られたパルプスラリーについて、TAPPIスタンダードシートマシン(角型)にて坪量60g/mとなるように抄紙した。得られた湿紙を、ロールプレスにて線圧15kg/cmでプレス脱水した。次いで、回転型乾燥機で110℃において4分間乾燥し、23℃、50%R.H.の条件下に24時間調湿して、手抄きシートを作成した。得られた手抄きシートの湿潤紙力強度(裂断長:Km)をJIS P8135に準じて測定した。
(Wet paper strength)
The pulp (L-BKP / N-BKP = 1/1) was disaggregated, and 0.4% (vs. pulp solid content conversion) of the above-mentioned crosslinking reaction product was added to the pulp slurry beaten until the filtrate amount reached 500 ml. . The pulp slurry thus obtained was paper-made with a TAPPI standard sheet machine (square) so as to have a basis weight of 60 g / m 2 . The obtained wet paper was press dehydrated with a roll press at a linear pressure of 15 kg / cm. Subsequently, it dried for 4 minutes at 110 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. The hand-sheet was prepared by adjusting the humidity for 24 hours under the above conditions. The wet paper strength (breaking length: Km) of the obtained handsheet was measured according to JIS P8135.

表7から、各実施例の変性物を含有する本発明の湿潤紙力剤は、比較例のものに比べて、湿潤強度を向上させうることが明らかである。
From Table 7, it is clear that the wet paper strength agent of the present invention containing the modified product of each example can improve the wet strength as compared with the comparative example.

Claims (7)

ジカルボン酸成分およびポリアルキレンポリアミン成分を縮合させてなるポリアミドポリアミン縮合物であって、該ジカルボン酸成分中に重合ロジンおよび/または重合ロジン低級エステルを20モル%以上含有するものであることを特徴とするポリアミドポリアミン縮合物(A)。 A polyamide polyamine condensate obtained by condensing a dicarboxylic acid component and a polyalkylene polyamine component, wherein the dicarboxylic acid component contains 20 mol% or more of a polymerized rosin and / or a polymerized rosin lower ester. Polyamide polyamine condensate (A). 前記重合ロジンおよび/または重合ロジン低級エステルが二量化ロジンおよび/または二量化ロジン低級エステルを40重量%以上含有するものである請求項1記載のポリアミドポリアミン縮合物(A)。 2. The polyamide polyamine condensate (A) according to claim 1, wherein the polymerized rosin and / or polymerized rosin lower ester contains 40% by weight or more of dimerized rosin and / or dimerized rosin lower ester. 請求項1または2に記載のポリアミドポリアミン縮合物(A)とエピハロヒドリンとを反応させて得られるポリアミドポリアミン架橋性変性物(B)。
A polyamide polyamine crosslinkable modified product (B) obtained by reacting the polyamide polyamine condensate (A) according to claim 1 or 2 with an epihalohydrin.
請求項1または2記載のポリアミドポリアミン縮合物(A)を含んでなるエポキシ樹脂用硬化剤。 A curing agent for epoxy resin comprising the polyamide polyamine condensate (A) according to claim 1 or 2. 請求項4に記載のエポキシ樹脂用硬化剤を用いてエポキシ樹脂を硬化させて得られるエポキシ樹脂硬化物。 The epoxy resin hardened | cured material obtained by hardening an epoxy resin using the hardening | curing agent for epoxy resins of Claim 4. 請求項3に記載のポリアミドポリアミン架橋性変性物(B)を含んでなる水性接着剤組成物。 An aqueous adhesive composition comprising the polyamide polyamine crosslinkable modified product (B) according to claim 3. 請求項3に記載のポリアミドポリアミン架橋性変性物(B)を含んでなる湿潤紙力剤。
A wet paper strength agent comprising the polyamide polyamine crosslinkable modified product (B) according to claim 3.
JP2012200307A 2012-09-12 2012-09-12 Polyamide polyamine condensate, polyamide polyamine crosslinkable modified product, curing agent for epoxy resin, cured epoxy resin, aqueous adhesive composition and wet paper strength agent Expired - Fee Related JP6048801B2 (en)

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US3778394A (en) * 1972-08-24 1973-12-11 Gen Mills Chem Inc Polymeric fatty acid polyamide modified with a rosin adduct
JPS5710131B2 (en) * 1974-03-15 1982-02-25
JPS5137959B2 (en) * 1974-05-30 1976-10-19
JPS6054439B2 (en) * 1975-09-29 1985-11-29 ハーキユリーズ・インコーポレーテツド Composition for paper size
CA2086487C (en) * 1991-12-31 1999-02-16 Ian A. Pudney Cationic polyamines useful as drainage aids and stabilizers for rosin-based sizing agents
JP2002201266A (en) * 1999-12-21 2002-07-19 Sumitomo Chem Co Ltd Water-soluble thermosetting resin and paper-strength- at-wet enhancer having this resin as effective component
JP2002173889A (en) * 2000-12-08 2002-06-21 Kindai Kagaku Kogyo Kk Dispersant for cation-type rosin emulsion sizing agent
JP5714442B2 (en) * 2010-12-24 2015-05-07 富士フイルム株式会社 POLYAMIDE POLYMER AND PROCESS FOR PRODUCING THE SAME, RESIN COMPOSITION, MOLDED BODY, FIBER, FILM AND POROUS FILM

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