JP2006225424A - Amino group-containing triazine modified novolak resin borate, method for producing the same and flame-retardant resin composition - Google Patents
Amino group-containing triazine modified novolak resin borate, method for producing the same and flame-retardant resin composition Download PDFInfo
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本発明は、アミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩及びその製造方法に関するものであり、当該変性樹脂を用いることにより、熱硬化性樹脂及び熱可塑性樹脂に高度な難燃性を賦与することができる。 The present invention relates to an amino group-containing triazine-modified novolak resin borate and a method for producing the same. By using the modified resin, high flame retardancy can be imparted to a thermosetting resin and a thermoplastic resin. it can.
熱硬化性樹脂及び熱可塑性樹脂は、機械的性質、耐熱性、電気的性質及び成形性などの点で優れた特性を有しており、電気用部品、自動車用部品、精密機械部品などの各種産業分野に広く使用されている。しかし、これらのほとんどは比較的に燃焼しやすい欠点を有していた。
従来、これらの熱硬化性樹脂及び熱可塑性樹脂に対して優れた難燃性を賦与するため、ハロゲン系難燃剤やリン系難燃剤の使用が知られているが、環境問題、特に燃焼時のダイオキシンなどの発生から、ハロゲンフリーやリンフリーの難燃剤の開発が強く要求されている。かかる難燃剤としてアミノ基含有トリアジン変性ノボラック樹脂を熱可塑性樹脂に用いることが提案されている(特許文献1)。しかし、該樹脂のみでは難燃性が不十分である。
また、難燃性や耐熱性などの向上を目的として、ホウ酸をノボラック型フェノール樹脂と反応させることによって得られるホウ酸変性フェノール樹脂をエポキシ樹脂硬化剤として用いる技術が提案されている(例えば、特許文献2)。しかしながら、ホウ素を導入することによる難燃性の向上は十分でなく、より高い効果を有する難燃化法が求められていた。
Conventionally, in order to impart excellent flame retardancy to these thermosetting resins and thermoplastic resins, the use of halogen-based flame retardants and phosphorus-based flame retardants is known, but environmental problems, particularly during combustion Development of halogen-free and phosphorus-free flame retardants is strongly demanded due to the generation of dioxins. As such a flame retardant, it has been proposed to use an amino group-containing triazine-modified novolak resin for a thermoplastic resin (Patent Document 1). However, the flame retardancy is insufficient with the resin alone.
In addition, for the purpose of improving flame retardancy and heat resistance, a technique using a boric acid-modified phenolic resin obtained by reacting boric acid with a novolac-type phenolic resin as an epoxy resin curing agent has been proposed (for example, Patent Document 2). However, the improvement of the flame retardancy by introducing boron is not sufficient, and a flame retarding method having a higher effect has been demanded.
本発明の目的は、難燃剤を始めとする各種の産業分野で有用なホウ酸系化合物で変性したアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩及びその製造方法を提供することにある。
本発明の他の目的は、上記アミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩を各種の熱硬化性樹脂及び熱可塑性樹脂に添加することにより、優れた難燃性樹脂組成物を提供することにある。
An object of the present invention is to provide an amino group-containing triazine-modified novolak resin borate modified with a boric acid compound useful in various industrial fields including a flame retardant and a method for producing the same.
Another object of the present invention is to provide an excellent flame retardant resin composition by adding the amino group-containing triazine-modified novolak resin borate to various thermosetting resins and thermoplastic resins. .
本発明者等は、トリアジン類のアミノ基及びフェノール樹脂の水酸基とホウ酸系化合物との高い反応性に着目して、前記目的を達成すべく、鋭意検討を重ねた結果、ホウ素を分子レベルで該樹脂に導入することにより、耐熱性に優れたアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩を見出した。
また、本発明者等は、上記樹脂ホウ酸塩を熱硬化性樹脂、例えばエポキシ樹脂、ノボラックフェノール樹脂又は熱可塑性樹脂、例えばポリスチレンやABS樹脂などに相溶叉は微分散させることによって、優れた難燃性樹脂組成物が得られることを見出し、本発明を完成するに至った。
即ち、本発明は、数平均分子量300〜1000のアミノ基含有トリアジン変性ノボラック樹脂を、ホウ素元素量がアミノ基1モルに対して0.1〜3モルの範囲となるようにホウ酸系化合物で変性してなるアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩に関する。
また、本発明は、前記数平均分子量300〜1000のアミノ基含有トリアジン変性ノボラック樹脂とホウ酸系化合物とを該樹脂の融点以上の温度で溶融混合して、叉はアミド系溶剤中に溶解して反応することからなるアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩の製造方法に関する。
The inventors of the present invention focused on the high reactivity between the amino groups of triazines and the hydroxyl groups of phenolic resins and boric acid compounds. By introducing it into the resin, an amino group-containing triazine-modified novolak resin borate excellent in heat resistance was found.
In addition, the inventors of the present invention are excellent by dispersing or finely dispersing the resin borate in a thermosetting resin such as an epoxy resin, a novolak phenol resin, or a thermoplastic resin such as polystyrene or ABS resin. The present inventors have found that a flame retardant resin composition can be obtained and have completed the present invention.
That is, the present invention modifies an amino group-containing triazine-modified novolak resin having a number average molecular weight of 300 to 1000 with a boric acid compound so that the amount of boron element is in the range of 0.1 to 3 moles per mole of amino groups. The present invention relates to an amino group-containing triazine-modified novolak resin borate.
In the present invention, the amino group-containing triazine-modified novolak resin having a number average molecular weight of 300 to 1000 and a boric acid compound are melt-mixed at a temperature equal to or higher than the melting point of the resin, or dissolved in an amide solvent. The present invention relates to a method for producing an amino group-containing triazine-modified novolak resin borate.
本発明でのアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩は、耐熱性に優れ、各種の熱硬化性樹脂及び熱可塑性樹脂の難燃剤として用いることができ、従来のハロゲン系、リン系難燃剤と比べて低毒性で環境に優しい。 The amino group-containing triazine-modified novolak resin borate in the present invention is excellent in heat resistance and can be used as a flame retardant for various thermosetting resins and thermoplastic resins, and with conventional halogen-based and phosphorus-based flame retardants. Less toxic and environmentally friendly.
本発明で用いるアミノ基含有トリアジン変性ノボラック樹脂（以下、ATN樹脂という）は、フェノール類とアミノ基含有トリアジン類とアルデヒト類とを反応して得られるアミノ基含有トリアジン変性ノボラック樹脂であって、該ノボラック樹脂が、フェノール類とアミノ基含有トリアジン類とアルデヒト類との縮合物との他に、アミノ基含有トリアジン類とアルデヒト類との縮合物、フェノール類とアルデヒト類との縮合物、未反応のフェノール類及びアミノ基含有トリアジン類を含んでいても構わない。また、用いられるATN樹脂の数平均分子量は300〜1000の範囲にあり、その分子中に平均0.5〜4個のアミノ基を有するものが最も好ましい。 The amino group-containing triazine-modified novolak resin (hereinafter referred to as ATN resin) used in the present invention is an amino group-containing triazine-modified novolak resin obtained by reacting phenols, amino group-containing triazines and aldehydes, In addition to the condensation product of phenols, amino group-containing triazines and aldehydes, the novolak resin is a condensation product of amino group-containing triazines and aldehydes, a condensation product of phenols and aldehydes, unreacted It may contain phenols and amino group-containing triazines. The number average molecular weight of the ATN resin used is in the range of 300 to 1000, and those having an average of 0.5 to 4 amino groups in the molecule are most preferable.
上記のATN樹脂を得るためのフェノール類としては、フェノール、ナフトール、ビスフェノールAなどの一価のフェノール性化合物、又はレゾルシン、キシレノールなどの二価のフェノール性化合物、又はピロガロール、ヒドロキシヒドロキノンなどの三価のフェノール性化合物、及びこれらフェノール性化合物のアルキル、カルボキシル、ハロゲン、アミンなどの誘導体などが挙げられる。また、これらのフェノール類は、単独又は二種以上組み合わせて使用できる。 Phenols for obtaining the above ATN resin include monovalent phenolic compounds such as phenol, naphthol and bisphenol A, or divalent phenolic compounds such as resorcin and xylenol, or trivalent compounds such as pyrogallol and hydroxyhydroquinone. Phenolic compounds, and derivatives of these phenolic compounds such as alkyl, carboxyl, halogen, and amine. Moreover, these phenols can be used individually or in combination of 2 or more types.
また、ATN樹脂に用いるアミノ基含有トリアジン類としては、特に限定されるものではなく、アミノ基含有トリアジン環を有すれば構造の如何を問わないが、メラミン、アセトグアナミン叉はベンゾグアナミンが好ましい。これらは単独又は二種以上の併用も可能である。 The amino group-containing triazines used in the ATN resin are not particularly limited, and any structure can be used as long as it has an amino group-containing triazine ring, but melamine, acetoguanamine or benzoguanamine is preferable. These can be used alone or in combination of two or more.
本発明のATN樹脂を得るためのアルデヒド類としては、例えばホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ヒドロキシフェニルアルデヒド、フルフラール、アクロレイン等が挙げられる。中でも、取り扱いの容易さの点からホルムアルデヒドが好ましい。ホルムアルデヒドとしては、特に限定するものではないが、代表的な供給源としてホルマリン、パラホルムアルデヒド等が挙げられる。 Examples of aldehydes for obtaining the ATN resin of the present invention include formaldehyde, acetaldehyde, benzaldehyde, hydroxyphenylaldehyde, furfural, acrolein and the like. Among these, formaldehyde is preferable from the viewpoint of easy handling. Although formaldehyde is not specifically limited, Formalin, paraformaldehyde, etc. are mentioned as a typical supply source.
本発明でのホウ酸系化合物としては、一般式(1)
Ｂ（ＯＲ）ｎ（ＯＨ）３−ｎ (1)
(式中、ｎは0〜3までの整数、RはＣｍＨ2ｍ+1のアルキル基であり、ｍは1〜10の整数を表す。)で表わされるホウ酸およびホウ酸エステル、ホウ酸エステルの部分重縮合物が用いられる。ホウ酸の具体的なものとしては、例えばオルトホウ酸、メタホウ酸、四ホウ酸、およびそれらの混合物であり、また、ホウ酸エステルの具体的なものとしては、例えばホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル等が挙げられる。これらのホウ酸及びホウ酸エステルは、単独又は２種以上組み合わせて使用できる。また、それらの部分加水分解物や部分重縮合物も用いることができる。上記の中ではホウ酸が最も好ましく用いられる。
なお、前記の部分重縮合物は、一般式(1)で表されるホウ酸エステルを、水、溶媒、及び必要により酸又は塩基触媒と共に混合攪拌する方法によって得ることができる。
As the boric acid compound in the present invention, the general formula (1)
B (OR) n (OH) 3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C m H 2m + 1 , and m is an integer from 1 to 10), boric acid and boric acid ester, boric acid Partial polycondensates of esters are used. Specific examples of boric acid include orthoboric acid, metaboric acid, tetraboric acid, and mixtures thereof, and specific examples of boric acid esters include trimethyl borate, triethyl borate, Examples include tripropyl borate and tributyl borate. These boric acid and boric acid ester can be used individually or in combination of 2 or more types. Moreover, those partial hydrolysates and partial polycondensates can also be used. Of these, boric acid is most preferably used.
The partial polycondensate can be obtained by a method in which the boric acid ester represented by the general formula (1) is mixed and stirred with water, a solvent, and, if necessary, an acid or a base catalyst.
本発明におけるATN樹脂ホウ酸塩の製造方法の一つは、ATN樹脂とホウ酸系化合物とを反応させて行う方法であって、その具体例としては、例えば次のようにして行うことができる。即ち、アミド系溶剤にホウ酸とATN樹脂を溶解させて攪拌しながら、80℃に昇温した。続いて、80℃加熱下、一定時間において反応を行う。得られた透明溶液をエパポレーターにより溶剤を留去する。このように得られた反応生成物をエーテルで数回繰り返し洗浄した後、真空乾燥により黄土色粉末のATN樹脂ホウ酸塩が得られる。 One of the methods for producing an ATN resin borate in the present invention is a method of reacting an ATN resin with a boric acid compound, and a specific example thereof can be performed as follows, for example. . Specifically, boric acid and ATN resin were dissolved in an amide solvent, and the temperature was raised to 80 ° C. while stirring. Subsequently, the reaction is carried out at 80 ° C. for a fixed time. The solvent is distilled off from the obtained transparent solution with an evaporator. The reaction product thus obtained is washed several times with ether, and then ATN resin borate as an ocher powder is obtained by vacuum drying.
上述のアミド系溶剤としては、N,N-ジメチルホルムアミド、N-メチルピロリドン、N,N-ジメチルアセトアミドなどが挙げられ、これらは単独又は二種以上の混合で使用できる。溶剤の使用量は、ホウ酸系化合物およびATN樹脂の合計100質量部に対して溶剤が300〜1500質量部となるように用いることが好ましい。 Examples of the amide solvent include N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide and the like, and these can be used alone or in a mixture of two or more. The amount of the solvent used is preferably such that the solvent is 300 to 1500 parts by mass with respect to 100 parts by mass in total of the boric acid compound and the ATN resin.
上述のATN樹脂ホウ酸塩の製造方法の製造条件として、ATN樹脂の中のアミノ基及びフェノール性水酸基とホウ酸系化合物のホウ素とのモル比が重要である。ホウ酸系化合物の比率を増やすと、高いホウ素含有量のATN樹脂ホウ酸塩が得られる。これに対してATN樹脂の比率を増やすと、より低いホウ素含有量のATN樹脂ホウ酸塩を得ることができる。一般的にATN樹脂の中のアミノ基及びフェノール性水酸基の合計１モルに対して、ホウ素が0.1〜3モルが好ましく、より好ましくは0.25〜2.5モル、特に好ましくは0.5〜2モルである。0.1モル未満の場合、得られたATN樹脂ホウ酸塩の難燃効果が不十分であり、3モルを超える場合、ホウ酸系化合物とアミド系溶剤との反応生成物を生じる恐れがあり、好ましくない。また、反応温度について、用いるポリアミン系化合物の種類によっては異なるが、一般的に20℃〜130℃が好ましく、より好ましくは25℃〜110℃であり、特に好ましくは30℃〜90℃である。反応時間は反応温度にもよるが、通常1〜30時間が好ましく用いられる。 As a production condition of the above-described production method of the ATN resin borate, the molar ratio of the amino group and phenolic hydroxyl group in the ATN resin to boron of the boric acid compound is important. Increasing the ratio of boric acid compound provides an ATN resin borate with a high boron content. On the other hand, when the ratio of the ATN resin is increased, an ATN resin borate having a lower boron content can be obtained. In general, the amount of boron is preferably 0.1 to 3 mol, more preferably 0.25 to 2.5 mol, particularly preferably 0.5 to 2 mol, based on 1 mol of the total of amino groups and phenolic hydroxyl groups in the ATN resin. When the amount is less than 0.1 mol, the flame retardant effect of the obtained ATN resin borate is insufficient. When the amount exceeds 3 mol, a reaction product of a boric acid compound and an amide solvent may be generated, which is preferable. Absent. Moreover, although it changes with kinds of polyamine type compound to be used about reaction temperature, generally 20 to 130 degreeC is preferable, More preferably, it is 25 to 110 degreeC, Especially preferably, it is 30 to 90 degreeC. Although the reaction time depends on the reaction temperature, usually 1 to 30 hours are preferably used.
上述のATN樹脂ホウ酸塩の製造方法のもう一つ具体例としては、溶剤を使用せず、ATN樹脂の融点以上の温度でホウ酸系化合物とATN樹脂との反応を行うことが例示できる。即ち、ATN樹脂を加熱溶融させて攪拌しながら、ホウ酸を加えて、一定温度と時間において反応を行う。得た透明融液を冷却した後、粉砕により黄土色粉末のATN樹脂ホウ酸塩が得られる。反応温度について、一般的にATN樹脂の融点より30℃以上が好ましく、より好ましくは融点より40℃以上であり、特に好ましくは融点より50℃以上である。反応時間は反応温度にもよるが、通常0.5〜10時間が好ましく用いられる。 As another specific example of the method for producing the ATN resin borate described above, the reaction between the boric acid compound and the ATN resin can be performed at a temperature equal to or higher than the melting point of the ATN resin without using a solvent. That is, boric acid is added while the ATN resin is heated and melted and stirred, and the reaction is performed at a constant temperature and time. After cooling the obtained transparent melt, an ocher ATN resin borate is obtained by grinding. The reaction temperature is generally preferably 30 ° C or higher than the melting point of the ATN resin, more preferably 40 ° C or higher than the melting point, and particularly preferably 50 ° C or higher than the melting point. Although the reaction time depends on the reaction temperature, usually 0.5 to 10 hours are preferably used.
本発明におけるATN樹脂ホウ酸塩の他の製造方法は、ホウ素変性トリアジン類とフェノール類とアルデヒド類との縮合反応を行わせる方法であって、例えば次のようにして行うことができる。ホウ素変性トリアジン類とフェノール類とアルデヒド類との混合物を、(ｉ)系のpHを5〜10に調整する工程、(ｉｉ)アルデヒド類が揮散しない条件下で該混合物を反応させる工程及び(ｉｉｉ)系内の反応水を除去する工程を含み、第1段反応として工程(ｉ)、工程(ｉｉ)及び工程(ｉｉｉ)を順次実施し、続いて第2段反応として工程(ｉｉ)及び工程(ｉｉｉ)を第1段反応より高い温度下に順次実施し、第3段反応として工程(ｉｉ)及び工程(ｉｉｉ)を第2段反応より高い温度下に順次実施し、更に必要に応じて第2段反応と第3段反応を繰り返し実施することによりATN樹脂ホウ酸塩が得られる。かかるフェノール類及びアルデヒド類とホウ素変性トリアジン類とのモル比が1:0.02〜0.15になるように配合することが好ましい。 Another method for producing an ATN resin borate according to the present invention is a method in which a condensation reaction of boron-modified triazines, phenols, and aldehydes is performed, and can be performed, for example, as follows. A mixture of boron-modified triazines, phenols and aldehydes, (i) adjusting the pH of the system to 5 to 10; (ii) reacting the mixture under conditions where aldehydes do not evaporate; and (iii) ) Including the step of removing the reaction water in the system, step (i), step (ii) and step (iii) are sequentially carried out as the first stage reaction, followed by step (ii) and step as the second stage reaction. (iii) is sequentially performed at a temperature higher than that of the first stage reaction, and steps (ii) and (iii) are sequentially performed at a temperature higher than that of the second stage reaction as a third stage reaction, and further if necessary. By repeating the second stage reaction and the third stage reaction, an ATN resin borate is obtained. It is preferable to blend such that the molar ratio of such phenols and aldehydes to boron-modified triazines is 1: 0.02 to 0.15.
上述のATN樹脂ホウ酸塩の製造に用いるホウ素変性トリアジン類は、アミノ基含有トリアジン類とホウ酸系化合物との反応によって得ることができる。例えば、水にメラミンとホウ酸を加え、攪拌しながら、一定温度と時間で反応させた。得た反応生成物を濾過により回収し、更に水とアセトンの順に洗浄した後、真空乾燥によりホウ酸メラミンの白色粉末が得られる。反応温度について、一般的に30℃〜140℃が好ましく、より好ましくは40℃〜120℃であり、特に好ましくは50℃〜100℃である。反応時間は反応温度にもよるが、通常1〜30時間が好ましく用いられる。また、アミノ基含有トリアジン類とホウ酸系化合物とのモル比については、一般的にアミノ基含有トリアジン類の中のアミノ基１モルに対して、ホウ素が0.1〜3モルが好ましく、より好ましくは0.3〜2.5モル、特に好ましくは0.5〜2モルである。 Boron-modified triazines used in the production of the ATN resin borate described above can be obtained by reaction of amino group-containing triazines with boric acid compounds. For example, melamine and boric acid were added to water and reacted at a constant temperature and time with stirring. The obtained reaction product is collected by filtration, washed with water and acetone in that order, and then dried in vacuo to obtain a white powder of melamine borate. About reaction temperature, 30 to 140 degreeC is generally preferable, More preferably, it is 40 to 120 degreeC, Most preferably, it is 50 to 100 degreeC. Although the reaction time depends on the reaction temperature, usually 1 to 30 hours are preferably used. The molar ratio of amino group-containing triazines and boric acid compounds is generally preferably 0.1 to 3 moles of boron, more preferably 1 mole of amino groups in amino group-containing triazines. 0.3 to 2.5 mol, particularly preferably 0.5 to 2 mol.
本発明でのATN樹脂ホウ酸塩は、分子中でATN樹脂中のアミノ基とホウ酸系化合物とでホウ酸塩を形成しているものであるが、ホウ酸系化合物の量及び反応条件によってはホウ酸系化合物叉はホウ酸塩基がATN樹脂中のフェノール性水酸基とも反応してホウ酸エステルを形成しているものと推察される。
尚、本発明のATN樹脂ホウ酸塩は、溶剤溶解性と加熱溶融性を持ち、熱硬化性樹脂及び熱可塑性樹脂に相溶叉は微分散させることにより、優れた難燃性をもたらせることができる。
The ATN resin borate in the present invention is a borate formed by the amino group in the ATN resin and the boric acid compound in the molecule, depending on the amount of boric acid compound and the reaction conditions. It is inferred that boric acid compounds or borate groups react with phenolic hydroxyl groups in the ATN resin to form borate esters.
The ATN resin borate of the present invention has solvent solubility and heat melting property, and can provide excellent flame retardancy by compatibilizing or finely dispersing in thermosetting resin and thermoplastic resin. be able to.
本発明の難燃性樹脂組成物に用いられる熱硬化性樹脂は特に限定されるものでなく市販されているものである。例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、アルキッド樹脂、ジアリルフタレート樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂などが挙げられる。この中、ATN樹脂ホウ酸塩がエポキシ樹脂の硬化剤としても用いられる。この場合、硬化反応によりATN樹脂ホウ酸塩が分子レベルにエポキシ樹脂に分散され、得られる硬化物の難燃効果が一層顕著なものになる。 The thermosetting resin used in the flame retardant resin composition of the present invention is not particularly limited and is commercially available. For example, epoxy resin, phenol resin, melamine resin, benzoguanamine resin, alkyd resin, diallyl phthalate resin, vinyl ester resin, unsaturated polyester resin, polyimide resin, and the like can be given. Of these, ATN resin borate is also used as a curing agent for epoxy resins. In this case, the ATN resin borate is dispersed in the epoxy resin at the molecular level by the curing reaction, and the flame retardant effect of the obtained cured product becomes more remarkable.
また、本発明の難燃性樹脂組成物に用いられる熱可塑性樹脂は特に限定されるものでなく市販されているものである。これらの中でも、ポリオレフィン系樹脂、ポリスチレン系樹脂、ABS樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリフェニレンエーテル系樹脂が好ましい。ポリオレフィン系樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂が挙げられる。また、ポリスチレン樹脂としては、スチレン並びにα-スチレン、ビニルトルエン等のスチレン誘導体の重合体及びそのゴム変性物、また、これらの単量体を主とし、これに共重合可能な単量体、例えばアクリロニトリル、ブタジエン、イソプレン等の一種以上を共重合したもの及びその水素添加物が挙げられる。 Moreover, the thermoplastic resin used for the flame-retardant resin composition of the present invention is not particularly limited and is commercially available. Among these, polyolefin resins, polystyrene resins, ABS resins, polyurethane resins, unsaturated polyester resins, polyamide resins, polycarbonate resins, and polyphenylene ether resins are preferable. Examples of the polyolefin resin include polyethylene resin and polypropylene resin. The polystyrene resin includes styrene, polymers of styrene derivatives such as α-styrene and vinyltoluene, and rubber-modified products thereof, and monomers mainly composed of these monomers, such as monomers copolymerizable therewith, such as Examples thereof include those obtained by copolymerization of one or more of acrylonitrile, butadiene, isoprene and the like and hydrogenated products thereof.
本発明の難燃性樹脂組成物には、更に用途、目的に応じて他の配合剤、例えばタルク、マイカ、炭酸カルシウムのような無機充填剤、カップリング剤あるいはガラス繊維、カーボン繊維などのような補強剤、難燃剤、難燃助剤、静電剤、安定剤、顔料、離型剤、エラストマーなどの耐襲撃改良剤などを配合することができる。 The flame retardant resin composition of the present invention may further include other compounding agents depending on applications and purposes, such as inorganic fillers such as talc, mica, and calcium carbonate, coupling agents, glass fibers, carbon fibers, and the like. Reinforcing agents, flame retardants, flame retardant aids, electrostatic agents, stabilizers, pigments, mold release agents, impact resistance improvers such as elastomers, and the like can be blended.
本発明の難燃性樹脂組成物の調製方法としては、一般に溶液法と溶融法が用いられる。溶液法としては、前述した樹脂とATN樹脂ホウ酸塩及びその他の成分を有機溶剤に溶解させ、得られる均一溶液を脱溶剤によりATN樹脂ホウ酸塩の相溶叉は微分散した樹脂組成物を得ることができる。また、溶融法としては、前述した樹脂とATN樹脂ホウ酸塩及びその他の成分を配合し、押出成形機や熱ロールによる溶融混練処理を行い、続いて冷却固化させ、適当な大きさに粉砕叉はペレット化して樹脂組成物とすることができる。 As a method for preparing the flame retardant resin composition of the present invention, a solution method and a melting method are generally used. As a solution method, a resin composition in which the above-described resin, ATN resin borate and other components are dissolved in an organic solvent, and the resulting homogeneous solution is dissolved or finely dispersed in ATN resin borate by solvent removal. Obtainable. Also, as a melting method, the above-mentioned resin, ATN resin borate and other components are blended, melt-kneaded with an extruder or a hot roll, then cooled and solidified, and pulverized to an appropriate size. Can be pelletized to form a resin composition.
本発明の難燃性樹脂組成物において、ATN樹脂ホウ酸塩と熱硬化性樹脂及び熱可塑性樹脂の配合比率は特に限定されるものではないが、熱硬化性樹脂又は熱可塑性樹脂100質量部に対してATN樹脂ホウ酸塩が5〜80質量部配合することが好ましい。ATN樹脂ホウ酸塩が5質量部を下回ると難燃効果が少なく、80質量部を上回ると得られる樹脂組成物の力学物性が低下する傾向となる。 In the flame-retardant resin composition of the present invention, the mixing ratio of the ATN resin borate, the thermosetting resin and the thermoplastic resin is not particularly limited, but the thermosetting resin or thermoplastic resin is 100 parts by mass. On the other hand, it is preferable to mix 5 to 80 parts by mass of ATN resin borate. If the ATN resin borate is less than 5 parts by mass, the flame retardant effect is small, and if it exceeds 80 parts by mass, the mechanical properties of the resulting resin composition tend to be reduced.
以下実施例により本発明を更に詳しく説明する。
また、以下の実施例において、熱硬化性樹脂組成物の酸素指数は酸素指数方式燃焼性試験機ON-2M(スガ試験器（株）製)を用いて、粉末法によって測定した。
熱可塑性樹脂組成物の酸素指数は酸素指数方式燃焼性試験機ON-2M(スガ試験器（株）製)を用いてJIS K7201 1999 によって測定した。
ホウ素含有量はPerkn Elmer社製 Optima 3300DVを用いて、ICPの測定を行い、予めホウ酸を用いて作成しておいた検量線により定量した。
Hereinafter, the present invention will be described in more detail with reference to examples.
In the following examples, the oxygen index of the thermosetting resin composition was measured by a powder method using an oxygen index method flammability tester ON-2M (manufactured by Suga Test Instruments Co., Ltd.).
The oxygen index of the thermoplastic resin composition was measured according to JIS K7201 1999 using an oxygen index method flammability tester ON-2M (manufactured by Suga Test Instruments Co., Ltd.).
The boron content was measured by ICP using an Optima 3300DV manufactured by Perkn Elmer, and quantified by a calibration curve prepared in advance using boric acid.
(実施例1)
コンデンサを備えたフラスコに、ATN樹脂フェノライトLA-1356(大日本インキ化学工業（株）製、窒素含有量19%、水酸基当量146、不揮発分60%のメチルエチルケトン溶液)固形105部とホウ酸51.6部とジメチルホルムアミド(DMF)480部とを仕込み、80℃にて攪拌しながら均一に溶解させた。引き続き、80℃で3時間反応を行った。そして、エパポレーターで溶剤を留去し、得た固体をエーテルで3回繰り返して洗浄した。更に70℃、2時間真空乾燥により、原料に対して収率90%で反応生成物の黄土色粉末1a 140.9部を得た。プラズマ発光分析によりホウ素含有率が5.5%であった。また、FT-IRのスベクトルからホウ酸塩基に由来する吸収が1440cm-1に観測され、目的の反応生成物ATN樹脂ホウ酸塩が得られたことを確認した。
(Example 1)
In a flask equipped with a condenser, ATN resin phenolite LA-1356 (manufactured by Dainippon Ink & Chemicals, Inc., nitrogen content 19%, hydroxyl group equivalent 146, methyl ethyl ketone solution with nonvolatile content 60%) solid 105 parts and boric acid 51.6 And 480 parts of dimethylformamide (DMF) were added and dissolved uniformly at 80 ° C. with stirring. Subsequently, the reaction was carried out at 80 ° C. for 3 hours. Then, the solvent was distilled off with an evaporator, and the obtained solid was washed with ether three times. Furthermore, by vacuum drying at 70 ° C. for 2 hours, 140.9 parts of an ocherous powder 1a as a reaction product was obtained with a yield of 90% based on the raw material. The boron content was 5.5% by plasma emission analysis. Further, absorption derived from borate group was observed at 1440 cm −1 from the FT-IR vector, confirming that the desired reaction product ATN resin borate was obtained.
(実施例2)
実施例2は、ホウ酸102.6部を用いた以外は実施例1と同様にしてATN樹脂ホウ酸塩粉末2aを合成した。プラズマ発光分析によりホウ素含有率が8.2%であった。
(Example 2)
In Example 2, ATN resin borate powder 2a was synthesized in the same manner as in Example 1 except that 102.6 parts of boric acid was used. The boron content was 8.2% by plasma emission analysis.
(実施例3)
攪拌機を備えたフラスコに、ATN樹脂フェノライトKA-7052-L2(大日本インキ化学工業（株）製、軟化点80℃) 100部とホウ酸20部とを仕込み、窒素気流下、攪拌しながら150℃に升温して溶融させた。引き続き、150℃で3時間反応を行った。得た融液を冷却固化させ、粉砕によりATN樹脂ホウ酸塩の黄土色粉末3a 115部を得た。プラズマ発光分析によりホウ素含有率が3.3%であった。また、FT-IRのスベクトルからホウ酸塩基に由来する吸収が1440cm-1に現れることを確認した。
(Example 3)
A flask equipped with a stirrer was charged with 100 parts of ATN resin phenolite KA-7052-L2 (Dainippon Ink Chemical Co., Ltd., softening point 80 ° C) and 20 parts boric acid while stirring under a nitrogen stream. It was heated to 150 ° C. and melted. Subsequently, the reaction was carried out at 150 ° C. for 3 hours. The obtained melt was cooled and solidified, and pulverized to obtain 115 parts of ATN resin borate ocher powder 3a. The boron content was 3.3% by plasma emission analysis. In addition, it was confirmed from the FT-IR vector that absorption derived from borate group appeared at 1440 cm −1 .
(実施例4)
コンデンサを備えたフラスコに、ホウ酸14.7部と水80部を仕込み、100℃に升温して均一に溶解させた。続いて、攪拌しながらメラミン粉末10部を添加し、100℃で6時間反応を行った。次に、濾過により固体分を回収し、水、アセトンの順で洗浄した。更に、70℃、2時間真空乾燥により、原料に対して収率69%でホウ酸メラミン1b 17.1部を得た。プラズマ発光分析によりホウ素含有率が9.1%であった。
(Example 4)
A flask equipped with a condenser was charged with 14.7 parts of boric acid and 80 parts of water, and the mixture was heated to 100 ° C. and dissolved uniformly. Subsequently, 10 parts of melamine powder was added with stirring, and the reaction was performed at 100 ° C. for 6 hours. Next, the solid content was collected by filtration and washed with water and acetone in this order. Furthermore, by vacuum drying at 70 ° C. for 2 hours, 17.1 parts of melamine borate 1b was obtained with a yield of 69% based on the raw material. The boron content was 9.1% by plasma emission analysis.
(実施例5)
フェノール37.7部、ホウ酸メラミン1b 10部に41.5%ホルマリン14.5部及びトリエチルアミン0.15部を加え、系のPHを8に調製し、発熱を注意しながら徐々に100℃まで升温した。100℃にて2時間反応させた後、常圧下にて水を除去しながら145℃まで2時間かけて升温した。次に環流下にて2時間反応させた後、常圧下にて水を除去しながら160℃まで2時間かけて升温した。更に環流下にて2時間反応させた後、常圧下にて水を除去しながら175℃まで2時間かけて升温した。次に90℃、14時間、真空下にて未反応のフェノールを除去し、原料に対して収率55%で反応生成物4a 29.3部を得た。プラズマ発光分析によりホウ素含有率が2.7%であった。また、FT-IRのスベクトルからホウ酸塩基に由来する吸収が1440cm-1に観測され、更には13C-NMR(D6-DMSO溶液)スベクトルからメラミンとフェノールとのメチレン架橋に由来するピーク(45.8ppm)が観測されており、目的の反応生成物ATN樹脂ホウ酸塩が得られたことを確認した。
(Example 5)
41.5% formalin 14.5 parts and triethylamine 0.15 parts were added to 37.7 parts of phenol, 10 parts of melamine borate, and 0.15 parts of triethylamine, and the pH of the system was adjusted to 8. After reacting at 100 ° C. for 2 hours, the mixture was warmed to 145 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 2 hours under reflux, the mixture was heated to 160 ° C. over 2 hours while removing water under normal pressure. The reaction was further continued under reflux for 2 hours, and then the mixture was warmed to 175 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under vacuum at 90 ° C. for 14 hours to obtain 29.3 parts of a reaction product 4a in a yield of 55% based on the raw material. The boron content was 2.7% by plasma emission analysis. Absorption derived from borate groups was observed at 1440 cm -1 from the FT-IR scan vector, and from the 13 C-NMR (D6-DMSO solution) scan vector, a peak derived from the methylene bridge between melamine and phenol. (45.8 ppm) was observed, confirming that the desired reaction product ATN resin borate was obtained.
(実施例6と比較例1)
ATN樹脂ホウ酸塩1a 28.5gをメタノール38gとメチルエチルケトン(MEK) 38gの混合溶液に加えて溶解させた。得た均一溶液にエピクロン850 37.5gを加え、攪拌混合した後、50℃で10時間の溶液状態での加熱処理を行い、エポキシ樹脂組成物溶液を得た。続いて該溶液をトレーに流延し、大気中、室温で12時間、溶媒キャストを行った後、熱風乾燥機にて50℃、60℃、70℃、80℃、90℃で各１時間乾燥し、更に、150℃で2時間の熱処理を行った。得られた試料を180μm以下の大きさに粉砕した。引き続き得た粉末を真空下70℃で2時間乾燥し、粉末状のエポキシ樹脂硬化物を得た。このようにして得られた硬化粉末を用いて、難燃性評価を行った。また、ATN樹脂ホウ酸塩の変わりにATN樹脂19.1部を用いた以外は実施例6と同一組成のエポキシ樹脂組成物である比較例1の硬化粉末も同様に調製した。表1に示したように、通常のATN樹脂を用いた比較例1の硬化粉末の酸素指数に比べ、ATN樹脂ホウ酸塩を使用した実施例6の硬化粉末の酸素指数が大幅に向上した。
(Example 6 and Comparative Example 1)
28.5 g of ATN resin borate 1a was added to and dissolved in a mixed solution of 38 g of methanol and 38 g of methyl ethyl ketone (MEK). 37.5 g of Epicron 850 was added to the obtained uniform solution, mixed with stirring, and then heated in a solution state at 50 ° C. for 10 hours to obtain an epoxy resin composition solution. Subsequently, the solution was cast on a tray, solvent casted in the atmosphere at room temperature for 12 hours, and then dried in a hot air dryer at 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C for 1 hour each. Further, heat treatment was performed at 150 ° C. for 2 hours. The obtained sample was pulverized to a size of 180 μm or less. Subsequently, the obtained powder was dried at 70 ° C. for 2 hours under vacuum to obtain a powdered epoxy resin cured product. Flame retardant evaluation was performed using the cured powder thus obtained. Further, a cured powder of Comparative Example 1 which was an epoxy resin composition having the same composition as Example 6 was prepared in the same manner except that 19.1 parts of ATN resin was used instead of ATN resin borate. As shown in Table 1, the oxygen index of the cured powder of Example 6 using the ATN resin borate was significantly improved as compared with the oxygen index of the cured powder of Comparative Example 1 using a normal ATN resin.
(実施例7,8と比較例2,3)
実施例7はポリスチレン(PS)(大日本インキ化学工業（株）製 クリアパクトTI-300)を使用し、実施例8はABS樹脂(東レ（株）製 トヨラック920)を使用した。これらの熱可塑性樹脂を、表2に示した割合でATN樹脂ホウ酸塩2aと混合し、シリンダー温度が230℃に設定された2軸押出機で混練造粒した後、圧縮成形機を用いて燃焼試験用試験片を得た。表1に得られた試験片を用いた難燃性評価結果を示す。また、ポリスチレン(比較例2)とABS樹脂(比較例3)の難燃性評価結果も併せて表2に示す。
(Examples 7 and 8 and Comparative Examples 2 and 3)
Example 7 used polystyrene (PS) (Clear Pact TI-300 manufactured by Dainippon Ink & Chemicals, Inc.), and Example 8 used ABS resin (Toyolac 920 manufactured by Toray Industries, Inc.). These thermoplastic resins were mixed with ATN resin borate 2a in the proportions shown in Table 2, kneaded and granulated with a twin-screw extruder set at a cylinder temperature of 230 ° C, and then compressed using a compression molding machine. A test piece for combustion test was obtained. Table 1 shows the results of flame retardancy evaluation using the obtained test pieces. Table 2 also shows the results of flame retardancy evaluation of polystyrene (Comparative Example 2) and ABS resin (Comparative Example 3).
Claims (12)
B(OR)n(OH)3-n
(式中、nは0〜3までの整数、RはCmH2m+1のアルキル基であり、mは1〜10の整数を表す。)である請求項1又は2に記載のアミノ基含有トリアジン変性ノボラック樹脂ホウ酸塩。 The boric acid compound has the general formula
B (OR) n (OH) 3-n
The amino group-containing triazine modification according to claim 1 or 2, wherein n is an integer of 0 to 3, R is an alkyl group of CmH2m + 1, and m is an integer of 1 to 10. Novolac resin borate.
12. The flame retardant resin composition according to claim 11, wherein the thermoplastic resin is at least one selected from the group consisting of polystyrene, polyurethane resin, ABS resin, polypropylene, polyethylene, polyamide, polycarbonate, and unsaturated polyester resin.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005037555A JP4403509B2 (en) | 2005-02-15 | 2005-02-15 | Amino group-containing triazine-modified novolak resin borate, method for producing the same, and flame-retardant resin composition |
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| JP2005037555A JP4403509B2 (en) | 2005-02-15 | 2005-02-15 | Amino group-containing triazine-modified novolak resin borate, method for producing the same, and flame-retardant resin composition |
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| Publication Number | Publication Date |
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| JP2006225424A true JP2006225424A (en) | 2006-08-31 |
| JP4403509B2 JP4403509B2 (en) | 2010-01-27 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679045A (en) * | 2018-12-27 | 2019-04-26 | 山东圣泉新材料股份有限公司 | A kind of rubber for tire novel green reinforced resin and combinations thereof |
| CN117070126A (en) * | 2023-09-28 | 2023-11-17 | 北京景泰消防科技有限公司 | Corrosion-resistant water-based fireproof paint and preparation method thereof |
| CN117210043A (en) * | 2023-10-19 | 2023-12-12 | 青岛恩泽化工有限公司 | Water-based flash rust prevention agent and preparation method thereof |
-
2005
- 2005-02-15 JP JP2005037555A patent/JP4403509B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679045A (en) * | 2018-12-27 | 2019-04-26 | 山东圣泉新材料股份有限公司 | A kind of rubber for tire novel green reinforced resin and combinations thereof |
| CN117070126A (en) * | 2023-09-28 | 2023-11-17 | 北京景泰消防科技有限公司 | Corrosion-resistant water-based fireproof paint and preparation method thereof |
| CN117070126B (en) * | 2023-09-28 | 2024-03-05 | 北京景泰消防科技有限公司 | Corrosion-resistant water-based fireproof paint and preparation method thereof |
| CN117210043A (en) * | 2023-10-19 | 2023-12-12 | 青岛恩泽化工有限公司 | Water-based flash rust prevention agent and preparation method thereof |
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| JP4403509B2 (en) | 2010-01-27 |
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