JP2007023237A - Crosslinking agent comprising halogenated alkylphenol-formaldehyde copolycondensation resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin crosslinking agent having a lower softening point than a crosslinking temperature of a rubber, excellent in the dispersibility into the rubber and in the blocking resistance, and reduced in the amount of remaining alkylphenol as a raw material. <P>SOLUTION: The resin crosslinking agent is produced by controlling its softening point to 85-115°C by giving a 1-30 wt.% plasticizer to a halogenated alkylphenol-formaldehyde copolycondensation resin containing less than 1.0% remaining alkylphenol as a raw material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a resin crosslinking agent comprising a halogenated alkylphenol-formaldehyde cocondensation resin containing a plasticizer.

Conventionally, flaky or particulate resol-type alkylphenol-formaldehyde cocondensation resins have been used as the resin crosslinking agent, but it is known that the dispersibility in rubber is poor. In order to sufficiently disperse the resin cross-linking agent in the rubber, it is preferable to knead at a temperature equal to or higher than the softening point of the resin. However, when the kneading temperature is 120 ° C. or higher, the rubber cross-linking reaction starts and a uniform rubber composition is obtained. Cannot be obtained. For this reason, a resin crosslinking agent having a softening point of 115 ° C. or lower is generally used.

It is known that the resin cross-linking agent is used in the form of fine powder or the softening point of the resin cross-linking agent is lowered, so that dispersibility is improved. Will not be able to withstand actual use.
As a method for measuring the resin cross-linking agent, preventing dust in the kneading operation step with the rubber, and improving the resin cross-linking agent, a method of creating a master batch of the resin cross-linking agent and rubber is disclosed. (Patent Document 1)

  On the other hand, prevention of environmental pollution has become a social issue in recent years, and reduction of impurities, residual raw materials and residual solvents in products has been demanded. In the production of the resin cross-linking agent, it is difficult to separate and reduce the residual amount of the alkylphenol as a raw material, and it is preferable from the viewpoint of production cost to reduce the residual amount by a method that completes the condensation reaction as much as possible. However, this method inevitably has a drawback that the softening point of the obtained resin cross-linking agent is increased and the dispersibility in rubber is lowered.

JP-A-7-173202

The object of the present invention is that the softening point is lower than the crosslinking reaction temperature of rubber, the dispersibility in rubber, the crosslinking performance of rubber and the blocking resistance during storage of the resin crosslinking agent have the same performance as conventional products, and It is to provide a resin cross-linking agent that is greatly reduced in terms of residual solvent and residual unreacted alkylphenol.

As a result of intensive studies aimed at solving the problems, the present inventors have found that the object of the present invention can be achieved by adding a plasticizer to the halogenated alkylphenol / formaldehyde cocondensation resin.

The present invention will be described in detail below.
The resin crosslinking agent of the present invention can be applied to all rubbers capable of sulfur crosslinking, and specific rubbers include natural rubber, SBR, isoprene rubber, NBR, butyl rubber, EPDM, CR and the like.

（Ｘはハロゲン元素、Ｚはハロゲン元素又は水酸基、Ｒは水素又はアルキル基である。） The halogenated alkylphenol / formaldehyde cocondensation resin used in the present invention is a resin obtained by halogenating a resol type alkylphenol / formaldehyde cocondensation resin with a halogenating agent, and the main component is represented by the formula (4).

(X is a halogen element, Z is a halogen element or a hydroxyl group, and R is hydrogen or an alkyl group.)

  The halogenated alkylphenol / formaldehyde cocondensation resin used in the present invention is, for example, an alkylphenol / formaldehyde cocondensation resin that can be synthesized by a known method described in Plastic Materials Course 15 “Phenolic Resin” (published by Nikkan Kogyo Shimbun). And an alkyl group (R) having 1 to 20 carbon atoms is preferably used. As the molecular weight of the halogenated cocondensation resin, those having a polystyrene-reduced weight average molecular weight of 1000 to 5000 are usually used. From the viewpoint of preventing environmental pollution, it is preferable that the residual amount of alkylphenol as a raw material and the residual amount of the solvent used for the reaction in the alkylphenol / formaldehyde cocondensation resin is smaller, and specifically, less than 1% by weight respectively. Used to select.

Examples of the halogenated alkylphenol / formaldehyde cocondensation resin compound used in the present invention include, for example, cresol / formaldehyde cocondensation resin, ethylphenol / formaldehyde cocondensation resin, butylphenol / formaldehyde cocondensation resin, octylphenol / formaldehyde cocondensation resin, butylphenol Examples include halogenated resins such as chlorine, bromine and iodine of resol type cocondensation resins such as octylphenol / formaldehyde cocondensation resin. Commercially available products include, for example, Tacrol 250 (brominated alkylphenol / formaldehyde cocondensation resin Taoka Chemical Co., Ltd.) Manufactured)) and the like.

  The content of the plasticizer in the halogenated alkylphenol / formaldehyde cocondensation resin of the present invention is 1 to 30% by weight, and 2 to 20% by weight is a preferred range. If the content of the plasticizer is less than 1% by weight, the effect of reducing the softening point is not recognized, and if it exceeds 30% by weight, the co-condensation resin of the present invention is blocked, and the hardness of the crosslinked rubber is reduced. Invited, not preferable.

（Ｒ_１は置換基を有していてもよい炭素数４〜１０の脂肪族基、Ｒ_２は炭素数１〜３のアルキレン基、Ｒ₃は炭素数４〜１３のアルキル基であり、ｘは、０〜９の整数を表わし、かつ４≦（Ｒ_２の炭素数）×Ｘ＋（Ｒ₃の炭素数）≦１３である。ｍは１〜３の整数を表し、ｍが２〜３の場合、Ｒ₂、Ｒ₃及びｘの組み合わせは、同一であっても異なっていてもよい。）

（Ｒ₄は置換基を有していてもよいベンゼン骨格１個を有する芳香族基であり、ｎは２〜４の整数を表す。Ｒ_２、Ｒ₃、ｘは前記と同じ意味を表わし、かつ４≦（Ｒ_２の炭素数）×Ｘ＋（Ｒ₃の炭素数）≦１３である。ｎは２〜４の整数を表し、Ｒ₂、Ｒ₃及びｘの組み合わせは、同一であっても異なっていてもよい。）

（Ｒ_２、Ｒ₃、ｘは前記と同じ意味を表わし、かつ４≦（Ｒ_２の炭素数）×Ｘ＋（Ｒ₃の炭素数）≦１３である。Ｒ₂、Ｒ₃及びｘの組み合わせは、同一であっても異なっていてもよい。）で表される化合物からなる群から選ばれる少なくとも１種が含まれることが好ましく、式（１）で表わされる化合物としては、例えば、２−エチルヘキシルオレート、ブトキシエチルオレート等の脂肪族モノカルボン酸エステルおよびその誘導体、ジイソブチルアジペート、ジブチルアジペート、ジ（２−エチルヘキシル）アジペート、ジイソデシルアジペート、ジイソトリデシルアジペート、ジメチルアゼレート、ジイソブチルアゼレート、ジブチルアゼレート、ジ（２−エチルヘキシル）アゼレート、ジイソデシルアゼレート、ジイソトリデシルアゼレート、ジメチルセバケート、ジイソブチルセバケート、ジブチルセバケート、ジ（２−エチルヘキシル）セバケート、ジイソデシルセバケート、ジイソトリデシルセバケート、ジブトキシエトキシエチルアジペート等の脂肪族ジカルボン酸エステルおよびその誘導体、アセチルトリブチルシトレート等の脂肪族トリカルボン酸エステルおよびその誘導体が挙げられる。 式（２）で表わされる化合物としては、例えば、ジブチルフタレート、ジイソブチルフタレート、ジ（２−エチルヘキシル）フタレート、ジイソデシルフタレート、ジイソトリデシルフタレート等の芳香族ジカルボン酸エステルおよびその誘導体、トリ（２−エチルヘキシル）トリメリテート等の芳香族トリカルボン酸エステルおよびその誘導体、テトラ（２−エチルヘキシル）ピロメリテート等の芳香族テトラカルボン酸エステルおよびその誘導体が挙げられる。 式(３)で表わされる化合物としては、例えば、トリブチルフォスフェート、トリ（２−エチルヘキシル）フォスフェート、トリ（ブトキシエチル）フォスフェート、２−エチルヘキシル−ジフェニルフォスフェート等のリン酸エステルが挙げられ、式（１）〜（３）で表わされる化合物の中でもジ（２−エチルヘキシル）フタレート、ジ（２−エチルヘキシル）セバケート、ジブトキシエトキシエチルアジペート、トリ（２−エチルヘキシル）ホスフェートがより好ましく、トリ（２−エチルヘキシル）ホスフェートおよびジ（２−エチルヘキシル）セバケートが更に好ましい。 The plasticizer in the present invention is not particularly limited, but those having good compatibility with both the halogenated alkylphenol-formaldehyde cocondensation resin and the rubber are preferable.
Specific examples of the plasticizer include aliphatic carboxylic acid derivatives, aromatic carboxylic acid derivatives, and phosphoric acid derivatives. Examples of the aliphatic carboxylic acid derivatives include aliphatic monocarboxylic acid esters, aliphatic dicarboxylic acid esters, fatty acids. Group tricarboxylic acid esters and derivatives thereof. Examples of aromatic carboxylic acid derivatives include aromatic dicarboxylic acid esters, aromatic tricarboxylic acid esters, aromatic tetracarboxylic acid esters, and derivatives thereof. Examples of phosphoric acid derivatives include phosphoric acid esters.
Among the plasticizers, the formulas (1) to (3)

(R ₁ is an optionally substituted aliphatic group having 4 to 10 carbon atoms, R ₂ is an alkylene group having 1 to ₃ carbon atoms, R ₃ is an alkyl group having 4 to 13 carbon atoms, and x Represents an integer of 0 to 9, and 4 ≦ (carbon number of R ₂ ) × X + (carbon number of R ₃ ) ≦ 13, m represents an integer of 1 to 3, and m is 2 to 3. In this case, the combination of R ₂ , R ₃ and x may be the same or different.)

(R ₄ is an aromatic group having one optionally substituted benzene skeleton, and n represents an integer of 2 to 4. R ₂ , R ₃ and x represent the same meaning as described above, And 4 ≦ (carbon number of R ₂ ) × X + (carbon number of R ₃ ) ≦ 13, n represents an integer of 2 to 4, and the combination of R ₂ , R ₃ and x may be the same. May be different.)

(R ₂ , R ₃ , and x have the same meaning as described above, and 4 ≦ (the number of carbons in R ₂ ) × X + (the number of carbons in R ₃ ) ≦ 13. The combination of R ₂ , R _3, and x is And at least one selected from the group consisting of compounds represented by formula (1) is preferable, and examples of the compound represented by formula (1) include 2-ethylhexyl. Aliphatic monocarboxylic acid esters such as oleate and butoxyethyl oleate and derivatives thereof, diisobutyl adipate, dibutyl adipate, di (2-ethylhexyl) adipate, diisodecyl adipate, diisotridecyl adipate, dimethyl azelate, diisobutyl azelate, dibutyl azelate , Di (2-ethylhexyl) azelate, diisodecylazelate, diisotridecyla Aliphatic dicarboxylic acid esters and derivatives thereof such as rate, dimethyl sebacate, diisobutyl sebacate, dibutyl sebacate, di (2-ethylhexyl) sebacate, diisodecyl sebacate, diisotridecyl sebacate, dibutoxyethoxyethyl adipate, acetyltributyl Examples thereof include aliphatic tricarboxylic acid esters such as citrate and derivatives thereof. Examples of the compound represented by the formula (2) include aromatic dicarboxylic acid esters such as dibutyl phthalate, diisobutyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, diisotridecyl phthalate, and derivatives thereof, and tri (2-ethylhexyl). ) Aromatic tricarboxylic acid esters such as trimellitate and derivatives thereof, and aromatic tetracarboxylic acid esters such as tetra (2-ethylhexyl) pyromellitate and derivatives thereof. Examples of the compound represented by the formula (3) include phosphate esters such as tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (butoxyethyl) phosphate, 2-ethylhexyl-diphenyl phosphate, Among the compounds represented by the formulas (1) to (3), di (2-ethylhexyl) phthalate, di (2-ethylhexyl) sebacate, dibutoxyethoxyethyl adipate, and tri (2-ethylhexyl) phosphate are more preferable, and tri (2 More preferred are -ethylhexyl) phosphate and di (2-ethylhexyl) sebacate.

The simplest method for mixing the halogenated alkylphenol / formaldehyde cocondensation resin and the plasticizer is to uniformly dissolve the plasticizer in the organic solvent solution of the halogenated alkylphenol / formaldehyde cocondensation resin and then distill the organic solvent off. Although it is a method, the method of mixing with a plasticizer without using an organic solvent at the temperature more than the softening point of resin is also possible.
The softening point of the resin cross-linking agent of the present invention is determined by the molecular weight of the condensation resin, the amount of residual alkylphenol, the amount of residual solvent, the amount of plasticizer added, and the softening point of the resin cross-linking agent is 85 to 115 ° C. The thing of -110 degreeC is preferable. When the softening point is lower than 85 ° C., mutual adhesion between resins tends to occur during storage. Therefore, it becomes necessary to store the resin cross-linking agent of the present invention at a low temperature. When the softening point is higher than 115 ° C., when the rubber compound is prepared. The kneading temperature becomes high and the rubber cross-linking reaction is partially initiated, resulting in a deterioration in the quality of the compound.

Although there is no restriction | limiting in particular in the usage-amount of the resin crosslinking agent of this invention, Usually, 1-50 weight part with respect to 100 weight part of rubber | gum, Preferably 3-30 weight part is used.
The resin cross-linking agent of the present invention can be used in combination with cross-linking accelerators such as CR, tin chloride, benzenesulfonic acid, calcium oxide, and molecular sieve.

As the crosslinking temperature when the resin crosslinking agent of the present invention is used, the same temperature region as that of the conventional resin crosslinking agent can be applied. Specifically, an appropriate temperature according to the type of rubber is selected at 120 to 230 ° C.
The resin cross-linking agent of the present invention is suitably used for rubber products and TPE products used in medicine plugs, bladders, condenser packings, tire tubes, inner liners, hoses, tubes, gaskets, automobile interior materials, home appliance parts, etc. .

According to the present invention, the softening point is lower than the crosslinking reaction temperature of rubber, the dispersibility to rubber, the crosslinking performance of rubber and the blocking resistance during storage of the resin crosslinking agent have the same performance as the conventional product, and A resin cross-linking agent having a greatly reduced residual solvent and residual unreacted alkylphenol is obtained.

The details of the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited by these examples.

The resin crosslinking agent was evaluated by the following method.
"Measurement of residual solvent and residual alkylphenol"
0.1 g of anisole as an internal standard substance was added to 1 g of a resin crosslinking agent, dissolved in 20 ml of acetone, and measured by gas chromatography.
"Measurement of softening point"
JIS K2207 compliant "Measurement of blocking resistance"
A flake-shaped resin cross-linking agent is put into a cylinder with a diameter of 4 cm so as to have a thickness of 3 cm, a plastic plate with a thickness of 1 mm and a diameter of 4 cm and a load of 360 g are placed on the top, and left in an oven at 45 ° C. for one week. Later, the blocking state of flakes was observed. Those having a blocking portion of 5% or more were evaluated as x.
"Measurement of dispersibility"
Using a Toyo Seiki Lab Plast Mill roller mixer (chamber capacity 60 cc), 50 g of a rubber compound having the following composition was prepared by kneading at a set temperature of 90 ° C. for 15 minutes. The obtained compound was formed into a sheet having a thickness of 0.5 mm with a roll, and the presence or absence of aggregates was visually observed. The thing without an aggregate was made into dispersibility (circle), and the thing with an aggregate was made into dispersibility x.
<Formulation> Polycerbutyl 402 100 parts by weight HAF carbon 50 parts by weight Stearic acid 1 part by weight Zinc white 5 parts by weight Resin cross-linking agent 40 parts by weight "Measurement of cross-linking characteristics with an oscillating rheometer"
Uses a rotary rheometer manufactured by Toyo Seiki Seisakusho.
Measured at a measurement temperature of 180 ° C and an amplitude angle of 3 °.

According to a known method, p-octylphenol, which is one of formaldehyde and alkylphenols, is used as a raw material, a resole resin having a residual amount of p-octylphenol of less than 1.0% is synthesized using an alkali catalyst, and toluene is added under reduced pressure. Distilled off and reacted with hydrogen bromide to obtain a brominated alkylphenol-formaldehyde cocondensation resin. Subsequently, 8 parts by weight of tri (2-ethylhexyl) phosphate as a plasticizer was added to the co-condensation resin with respect to 100 parts by weight of the resin to obtain a resin crosslinking agent A.
The obtained resin cross-linking agent A was measured for residual solvent amount, residual p-octylphenol amount, softening point, blocking resistance and dispersibility, and listed in Table 1.
Using a roll of compounded compound of Policer butyl 402 (100 parts by weight), HAF carbon (50 parts by weight), stearic acid (1 part by weight), zinc white (5 parts by weight), and resin cross-linking agent A (12 parts by weight) And prepared by a conventional kneading method. The resulting compound was measured for cross-linking properties with an oscillating rheometer at 180 ° C. for 60 minutes and listed in Table 2.

  Resin crosslinking agent B was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 4 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.

  Resin crosslinking agent C was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 2 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.

(Comparative Example 1)
Resin crosslinking agent D was synthesized in the same manner as in Example 1 except that tri (2-ethylhexyl) phosphate was not blended. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.

(Comparative Example 2)
Resin crosslinking agent E was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 20 parts by weight. Table 1 shows the results of measurement of the residual solvent amount, residual p-octylphenol amount, softening point, blocking resistance, and dispersibility of the obtained resin E.
With respect to the resin crosslinking agent E, the evaluation result of the blocking resistance was x, so the crosslinking characteristics with an oscillating rheometer were not measured.

Ｔ（１０）：加硫曲線から求められた、トルクの最大値と最小値との差の１０％に達するまでの時間（分）
Ｔ（９０）：加硫曲線から求められた、トルクの最大値と最小値との差の９０％に達するまでの時間（分）
ＭＬ ：加硫曲線から求められた、トルクの最小値（ｋｇ・ｃｍ）
ＭＨ ：加硫曲線から求められた、トルクの最大値（ｋｇ・ｃｍ）

T (10): Time (minutes) required to reach 10% of the difference between the maximum and minimum torque values determined from the vulcanization curve
T (90): Time (minutes) required to reach 90% of the difference between the maximum and minimum torque values determined from the vulcanization curve
ML: Minimum torque value (kg · cm) obtained from the vulcanization curve
MH: Maximum value of torque (kg · cm) obtained from vulcanization curve

Claims (3)

  Resin crosslinking agent characterized in that softening point of halogenated alkylphenol-formaldehyde cocondensation resin containing 1-30% by weight of plasticizer is 85-115 ° C The plasticizer is represented by the formulas (1) to (3)

(R ₁ is an optionally substituted aliphatic group having 4 to 10 carbon atoms, R ₂ is an alkylene group having 1 to ₃ carbon atoms, R ₃ is an alkyl group having 4 to 13 carbon atoms, and x Represents an integer of 0 to 9, and 4 ≦ (carbon number of R ₂ ) × X + (carbon number of R ₃ ) ≦ 13, m represents an integer of 1 to 3, and m is 2 to 3. In this case, the combination of R ₂ , R ₃ and x may be the same or different.)

(R ₄ is an aromatic group having one optionally substituted benzene skeleton, and n represents an integer of 2 to 4. R ₂ , R ₃ and x represent the same meaning as described above, And 4 ≦ (carbon number of R ₂ ) × X + (carbon number of R ₃ ) ≦ 13, n represents an integer of 2 to 4, and the combination of R ₂ , R ₃ and x may be the same. May be different.)

(R ₂ , R ₃ , and x have the same meaning as described above, and 4 ≦ (the number of carbons in R ₂ ) × X + (the number of carbons in R ₃ ) ≦ 13. The combination of R ₂ , R _3, and x is The resin cross-linking agent according to claim 1, comprising at least one selected from the group consisting of compounds represented by:   3. The resin crosslinking agent according to claim 1, wherein the content of unreacted alkylphenol in the halogenated alkylphenol-formaldehyde cocondensation resin is less than 1.0%.