JP2003201465A - Sealing material composition containing chemically modified 4c olefin polymer and organic solvent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing material composition for weatherstrips, effective for suppressing the swelling of the weatherstrip, free from dissolution with a cleaning liquid for the weatherstrip and the emission of odor and especially suitable for the combined use with the weatherstrip. <P>SOLUTION: The sealing material composition for a weatherstrip contains a 4C olefin polymer having an average molecular weight of 100-60,000, an oxygen-containing derivative of a 4C olefin polymer containing a terminal vinylidene group and having an average molecular weight of 100-60,000 and an oxygen-containing diluent having a solubility parameter defined by (MPa)<SP>1/2</SP>of 15-35. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealant composition used for weather strips made of an ethylene-propylene rubber composition.

[0002]

2. Description of the Related Art In a vehicle, the sound insulation from external noise in the passenger seat is improved, the airtightness is maintained to keep the temperature inside the passenger comfortably, the vibration of the window is suppressed, and the rain water flows into the passenger seat and the trunk. Various weather strips are used for protection. For example, weatherstrip sunroof, weatherstrip roofside,
These include weatherstrip / door outer, weatherstrip / drip, weatherstrip / trunk lid, door weatherstrip, weatherstrip / glass run, and weatherstrip for dead-fitting window.
The weather strip is also used for window frames of houses and the like, and is improved in sound insulation, airtightness, and vibration suppression in houses and the like.

Ethylene-propylene rubber, that is,
The ethylene propylene binary copolymer (hereinafter abbreviated as “EPM”) and the ethylene propylene non-conjugated diene ternary copolymer (hereinafter abbreviated as “EPDM”) have no unsaturated bond in the main chain. , Excellent in ozone resistance, heat aging resistance, weather resistance, etc. Even when compared with other rubber materials having excellent weather resistance such as chloroprene rubber (CR), the ethylene-propylene rubber can be blended with a large amount of inorganic filler such as calcium carbonate and clay, and therefore the cost is low. Is low, which is advantageous.

Both of them are capable of organic peroxide vulcanization, but EPDM is also capable of sulfur vulcanization, oxime vulcanization, phenol resin vulcanization and the like. For this reason, among ethylene-propylene rubber compositions, EPDM compositions have become the mainstream weather strip material. There are various embodiments of these compositions, and specific examples thereof include JP-A-5-171097 and JP-A-6-283.
70, JP-A-6-49296, JP-A-6-
107877, JP-A-7-145279,
The embodiments described in JP-A-8-3395, JP-A-11-80460 and the like can be mentioned.

These weather strips are usually used by fitting a holding channel portion provided in the weather strip into a frame provided in a vehicle body or a building, and a window (sunroof) glass.
Then, if necessary, a sealing material composition is filled in the gaps such as the retaining channel and the frame of the weather strip and / or the weather strip retaining channel and the window (sunroof) glass to maintain and improve various properties. Is going.

Examples of inexpensive sealing material compositions include:
A polymer of a C ₄ olefin having a specific molecular weight (for example, polybutene) as a sealing material, a mineral oil (for example, mineral terpene) as a diluent, and a granular inorganic material (for example, calcium carbonate, as a flow characteristic adjusting material).
Compositions containing talc) are known. In addition to these, the components added include a viscosity modifier, an anti-sagging agent,
Antioxidants, weathering agents, pigments, lubricants, heat stabilizers and the like can be mentioned.

As a sealing material, a polymer of a C ₄ olefin having a specific molecular weight is preferably used, because the polymer is extremely excellent in tackiness, moisture resistance and weather resistance. Further, it is because it has a property that it is not attacked by the window cleaning liquid (main component is methanol).

[0008]

However, since the C ₄ olefin polymer swells the ethylene-propylene rubber, it has the drawback of deforming the weather strip, and the (mineral) terpene has the disadvantage that the ethylene-propylene rubber is used. In addition to the problem of swelling, there is a problem of dissolving the adhesive to separate the weather strip, and in particular, a problem of generation of odor when exposed to a high temperature environment for a long time such as in a trunk room.

Further, in order to economically manufacture such a sealing material, a low viscosity product of a C ₄ olefin polymer is used as a base material and more inexpensive inorganic materials are added. Has been desired. However, it has become clear that the low viscosity polymer increases the above-mentioned drawback of deformation of the weatherstrip. In other words, it has become a technical problem today to solve the problems of conflicting properties of lowering the viscosity of the polymer and preventing deformation of the weather strip.

Therefore, a sealant composition containing a conventional C ₄ olefin polymer is
It is difficult to contribute to providing stable properties and a comfortable environment of the weather strip.

An object of the present invention is to provide a sealing composition for weatherstrip, which is suitable for use in combination with a weatherstrip, which suppresses swelling of the weatherstrip, does not elute even with a cleaning solution for the weatherstrip, and does not generate odor. Especially.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific C ₄ olefin polymer and an oxygen-containing derivative of the specific C ₄ olefin polymer (these are mainly used as a sealing material). Functioning) and an organic solvent having a specific solubility parameter, preferably an organic solvent having a specific solubility parameter and a specific chemical structure (mainly functioning as a diluent) is ethylene. The present invention has been completed by finding that the sealing material composition does not swell the weather strip made of the propylene-based rubber composition, is not eluted by the cleaning solution for the weather strip, and does not generate odor.

[0013]

That is, the present invention provides a C ₄ olefin polymer having an average molecular weight of 100 to 60,000, an oxygen-containing derivative of a C ₄ olefin polymer having a terminal vinylidene group and an average molecular weight of 100 to 60,000, And a sealing material composition for a weather strip, which comprises an oxygen-containing diluent having a solubility parameter represented by (MPa) ^1/2 in the range of 15 to 35.

The average molecular weight of the C ₄ olefin polymer and / or the oxygen-containing derivative of the C ₄ olefin polymer is
It can be 500 or more and 3000 or less. The C ₄
The repeating unit structure of the oxygen-containing derivative of the olefin polymer and / or the C ₄ olefin polymer can be an isobutene structure.

The terminal chemical structure of the oxygen-containing derivative of the C ₄ olefin polymer is epoxidized structure, aliphatic alcohol type hydroxyl group-containing structure, aromatic alcohol type hydroxyl group-containing structure, carboxylic acid type structure, maleic anhydride type structure, At least one selected from the group consisting of maleic anhydride ester derivative structures and these derivative structures can be used.

The terminal chemical structure of the oxygen-containing derivative of the C ₄ olefin polymer may be a phenol compound type structure.

The oxygen-containing diluent can be a vegetable oil or fat. The oxygen-containing diluent can be a vegetable oil having a hydroxyl group. The oxygen-containing diluent can be at least one selected from the group consisting of castor oil, its derivatives, rice oil and corn oil. The oxygen-containing diluent can be a vegetable oil containing vitamin Es.

[0018]

The present invention will be further described in detail.
The sealing material composition of the present invention, as a sealing material,
Average molecular weight of 100 or more and 60,000 or less [converted to polystyrene by GPC (gel permeation chromatography)]
C ₄ olefin polymer having a terminal vinylidene group and having an average molecular weight of 100 or more and 60,000 or less [in terms of polystyrene determined by GPC (gel permeation chromatography)] C ₄ olefin polymer oxygen derivative (hereinafter referred to as “oxygen derivative”) ) Is included.

As the oxygen-containing derivative, for example, an epoxidation product of a terminal vinylidene group (terminal chemical structure is an epoxidized structure), a hydroxylation product of a terminal vinylidene group,
Hydroformylation products of terminal vinylidene groups, carboxylation products of terminal vinylidene groups, etc .;

Reaction products of terminal vinylidene groups and aliphatic alcohol compounds (including aliphatic alcohols, glycols, propylene glycols, polyhydric alcohols, and ester derivatives and ether derivatives thereof) (terminals) Chemical structure is an aliphatic alcohol type hydroxyl group-containing structure);

Terminal vinylidene groups and aromatic alcohol compounds (phenols, naphthols, polyalcohols,
Reaction products with hydroxycarboxylic acids, cresols, and their derivatives (including ester derivatives and ether derivatives) (terminal chemical structure is aromatic alcohol type hydroxyl group-containing structure); terminal vinylidene group and carboxylic acid compound (monovalent A reaction product (including a carboxylic acid-type structure at the terminal chemical structure) with a carboxylic acid, an unsaturated divalent carboxylic acid, a polyvalent carboxylic acid, and ester derivatives thereof;

Reaction products of terminal vinylidene groups and maleic anhydride compounds (including maleic anhydride, succinic anhydride, succinic acid diester diol, succinic acid dimethyl ester, succinic acid diester diol, lactone derivatives) (terminal chemical structure) Is a maleic anhydride type structure);

An ester derivative of a reaction product of a terminal vinylidene group and maleic anhydride (an ester derivative type structure of which the terminal chemical structure is maleic anhydride);

Reaction product of terminal vinylidene group and ether compound (terminal chemical structure is etherified structure);

Included are these derivatives; and mixtures thereof. The oxygen-containing derivative is a C ₄ olefin polymer part having a high affinity for ethylene-propylene rubber,
It is characterized by having an end portion of an oxygen-containing structure having a low affinity for ethylene-propylene rubber. As is apparent from the examples described below, the introduction of oxygen atom causes ethylene-
The terminal portion having a low affinity for propylene rubber is C
_{4 It} is considered to have the function of relaxing / suppressing the swelling property of the olefin polymer in ethylene-propylene rubber.

The oxygen-containing derivative has a structure in which an oxygen-containing compound is added to the end of the C ₄ olefin polymer. The difference between the solubility parameter of the compound corresponding to this adduct (hereinafter referred to as "Sp value") and the Sp value of the ethylene-propylene rubber is about 15 in order to exhibit the swelling suppression effect of the sealing material containing the oxygen-containing derivative. is important. In the present specification, the unit of the Sp value is all (MPa) ^1/2 unit.

The C ₄ olefin polymer conventionally used as a sealing material has an Sp value of about 16, and since it has only a slight difference from the Sp value of the ethylene-propylene rubber, it is not suitable for weather strip application. Deformation of the weather strip was occurring.

Therefore, for example, in the case of an oxygen-containing derivative consisting of a reaction product obtained by adding phenol to a C ₄ olefin polymer, the phenol portion at the terminal oxygen-containing end increases the Sp value of the whole oxygen-containing derivative. It is possible to let. When the composition contains the above-described chemically modified oxygen-containing derivative of phenol, the oxygen-containing derivative is an oxygen-containing diluent (for example, rice oil: Sp value = 16.1, corn oil: Sp value = 16.2, Castor oil: Sp value = 18.2) forms a homogeneous phase when mixed with it, so that the effect of the sealing material can be enhanced.

According to the study by the present inventors, the Sp value is about 1
6 to 35, preferably 16 to 25, more preferably 1
It was found that the oxygen-containing derivative obtained by reacting the compounds of 7 to 22 has preferable properties. That is, the oxygen-containing derivative having an external structure to which a compound having an Sp value of less than 16 is added does not have a sufficient swelling suppressing effect on the weather strip made of the ethylene-propylene rubber composition,
Further, the oxygen-containing derivative having an external structure in which a compound having an Sp value of more than 35 is added tends to be eluted by methanol contained in the cleaning liquid of the weather strip.

The preferred C ₄ olefin polymer has an average molecular weight of 100 or more and 60,000 or less, preferably 500 or more and 3000 or less, and when it is less than 100 or more than 60,000, it is eluted by methanol contained in the detergent of the weather strip. Alternatively, a problem may occur in the gap filling process between the weather strip and the structure (glass or metal body, etc.). Molecular weight is GP
It can be determined by C analysis.

Average molecular weight of 10 having terminal vinylidene group
The oxygen-containing derivative of the C ₄ olefin polymer in the range of 0 or more and 60,000 or less means the average molecular weight of 100 or more and 60 or more.
It is produced via a known chemical reaction between a polymer having a terminal vinylidene group in a C ₄ olefin polymer of 000 or less and an oxygen-containing organic compound. Therefore, in order to efficiently obtain an oxygen-containing derivative, a terminal vinylidene group-containing C ₄
It is preferable to use a C ₄ olefin polymer having a high olefin polymer content as a raw material. C containing terminal vinylidene group
_{As a} method for producing a C ₄ olefin polymer containing a large amount of a ₄ olefin polymer, the present inventors have disclosed in Japanese Patent Laid-Open No. 10-3061
The method described in Japanese Patent No. 28 is exemplified.

In this method, isobutene alone or
When an olefin raw material composed of isobutene and butene-1 and butene-2 as appropriate is used and these are polymerized with a boron trifluoride-based catalyst, n-butene hardly copolymerizes with isobutene. A C ₄ olefin polymer containing a terminal vinylidene group can be obtained in an amount of 60 mol% or more based on the total moles of the combined polymer. The mol% of the C ₄ olefin polymer containing a terminal vinylidene group can be confirmed from the integrated quantitative value of the olefin attribution peak of 13 C-NMR measurement (for details, see JP-A-10-306128).

C produced according to the above-mentioned proposed method
_{Since the 4} olefin polymer contains almost no tertiary carbon in its molecule, which easily causes heat deterioration and oxidative deterioration, the sealing material containing the C ₄ olefin polymer also has excellent heat resistance and long-term stability. .

The production of the oxygen-containing derivative is carried out by arbitrarily selecting it from known reaction executing means. For example, regarding the epoxidation reaction, U.S. Pat.
Regarding the addition reaction of maleic anhydride, the European Polymer Journal of M. Tessier et al.
r. Polymer Journal), vol. 20, No. 3, 269
-Page 280 (1984).

Among the oxygen-containing derivatives, the epoxidation product of the terminal vinylidene group and the addition reaction product of the terminal vinylidene group and the phenol compound; the reaction is easy because of the balance between the reaction and the Sp value of the oxygen-containing end structure. The addition reaction product of the terminal vinylidene group and the maleic anhydride compound is preferred because of the variety of reaction products and the ease of derivative formation. That is, a maleic anhydride esterified derivative may be added, or it may be esterified after addition of maleic anhydride.

As the sealing material in the present invention, a highly pure oxygen-containing derivative may be obtained and used as it is, or the oxygen-containing derivative may be diluted with a known sealing material such as a C ₄ olefin polymer. You may use it.

When it is intended for industrial use, for example,
According to the method of Japanese Patent Laid-Open No. 10-306128,
C ₄ containing isobutene, butene-1, butene-2, etc.
An olefin raw material is used to perform a polymerization reaction to produce a mixture containing a predetermined mol% or more of a terminal vinylidene group-containing C ₄ olefin polymer, and subsequently, a C ₄ olefin polymer containing a terminal vinylidene group in the mixture. By reacting and converting the terminal vinylidene group of
It is efficient to obtain a C ₄ olefin polymer containing the oxygen-containing derivative of The mol% of the oxygen-containing derivative is 13C
It can be determined by -NMR measurement, 1H-NMR measurement, and TLC (thin layer chromatography method).

The oxygen-containing derivative mol% in the sealing material for exhibiting the swelling suppressing effect is defined by the specific chemical structure of the oxygen-containing terminal structure, the chemical structure of the ethylene-propylene rubber composition, the composition, the crosslinking density, Depending on the crosslinking method, for example, the effect appears at 5 mol% or more based on the total mol of the sealing material containing the C ₄ olefin polymer,
It is preferably 10 mol% or more, more preferably 20 mol% or more, and swelling of the weather strip hardly occurs.

The diluent in the sealant composition may be a viscosity / rheology adjustment of the whole sealant composition, a weather strip and a structure (glass or metal body, etc.).
And the viscosity rheology of the sealing material composition in the step of filling the voids between them, and the viscosity rheology of the inorganic filler in the step of dispersing the sealing material composition. Conventionally, mineral oil-based diluents have been used, and (mineral) terpen is a typical example.

The oxygen-containing diluent in the sealant composition according to the present invention has the conventional effect on the sealant containing a C ₄ olefin polymer and, in addition, has the affinity for the oxygen-containing derivative in the present invention. Therefore, the Sp value of the C ₄ olefin polymer is S
It is in the range of 15 which is almost equal to the p value (about 16) to the Sp value 35 of the oxygen-containing compound corresponding to the terminal structure of the oxygen-containing derivative, and contains oxygen.

The more preferable Sp range of the oxygen-containing diluent is 15 to 25. If the Sp value is more than 35, there may be a problem of elution with methanol contained in the cleaning solution such as a window cleaning agent. The reason why oxygen is preferred is not clear, and the present inventors believe that it is currently related to the affinity between the oxygen-containing derivative and the oxygen-containing diluent. It is not limited.

In the present invention, the Sp value of the diluent is approximated to the Sp value of the C ₄ olefin polymer in order to satisfy this requirement. On the other hand, in order to suppress the swelling of EPDM rubber (Sp value of about 15) which is mainly used as a weather strip material, an oxygen-containing functional group was introduced into the diluent to prepare EPDM rubber.
The affinity with rubber is reduced.

The composition of the sealant and the diluent in the sealant composition is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 30 parts by weight of the diluent per 100 parts by weight of the sealant. It can be a department. In the final sealant composition, a mixture 1 of both
20 to 70 parts by weight of another auxiliary material containing an inorganic filler as a main component may be further added to 00 parts by weight.

Preferred examples of the oxygen-containing diluent in the present invention are alcohol ester derivatives of aromatic polycarboxylic acids, higher dicarboxylic acids, ester derivatives of higher dicarboxylic acids, ethylene glycol derivatives, propion glycol (glycerin) derivatives or higher alcohols. Is. More preferably, of these, the boiling point is 200 ° C.
These are the above, and more preferably, those containing a hydroxyl group.

Since the organic solvent satisfying the above three conditions has a long chain portion having a high affinity for the C ₄ olefin polymer and a polar functional group having a low affinity, it has already been described in this respect. It is similar to the properties of oxygenated derivatives. Further, the action on ethylene-propylene rubber is considered to be similar to that of the oxygen-containing derivative. It is considered that the boiling point basically contributes to the reduction / prevention of odor generation.

Examples of preferable oxygen-containing diluents obtained from the natural world include vegetable oils and fats containing a propion glycol (glycerin) derivative as a main component. These are listed on pages 99 to 101 of the Oil and Fat Chemistry Handbook (Japan Oil Chemistry Association: Maruzen, 1990). Specific examples include soybean oil, sesame oil, corn oil, rapeseed oil, rice oil, camellia oil, castor oil, wheat germ oil, pumpkin seed oil, cottonseed oil and mixtures thereof.

Among these, soybean oil having a hydroxyl group,
Castor oil, corn oil, wheat germ oil, pumpkin seed oil, cottonseed oil and mixtures thereof are preferred. Among these, those having a high acetyl value are preferable, and, for example, castor oil is preferable.

Rapeseed oil containing a large amount of vitamin E (tocopherol) having antioxidant ability and having high stability,
Rice oil, corn oil, and mixtures thereof are also preferred examples.

In vegetable oils and fats, containing a hydroxyl group means
It means that one of the main components of the compound constituting the vegetable oil is a compound containing a hydroxyl group.

These may be used alone or as a mixture, or may be used in combination with a mineral oil type diluent such as (mineral) terpene.

When these vegetable fats and oils are used as a mixture, the blending ratio is (at least one selected from rapeseed oil, rice oil and corn oil): castor oil, 6: 4 to 10:
It can be zero.

The sealing material composition of the present invention is particularly suitable for use in combination with a weather strip used for window frames of vehicles and houses.

The sealant composition of the present invention contains a granular inorganic material, a viscosity modifier, an anti-sagging agent, an antioxidant, a weathering agent, a pigment, a lubricant, and a heat agent based on 100 parts by weight of the sealant and the diluent. Stabilizer, or a mixture thereof, is added to 20
70 parts by weight may be included.

[0054]Examples 1-12 and Comparative Examples 1-3 In order to clearly express the effect of the present invention, a terminal vinylidene group
It consists of a sealant containing an oxygen-containing derivative and an oxygen-containing diluent.
A sealant composition liquid according to the present invention, _Four Olef
A conventional sheath consisting of in-polymer and (mineral) terpen
A comparison was made with the liquid of the ring composition.

First, polybutene (HV-15, HV-300 and HV manufactured by Nippon Petrochemical Co., Ltd.), which is a typical example of a C ₄ olefin polymer sealing material used as a comparative product, is used.
V-1900 (each product name)], GP
The average molecular weight of each was determined by C. The results are shown in the table.

Subsequently, a high concentration C ₄ olefin polymer containing a vinylidene group terminal, which is a raw material for an oxygen derivative containing a vinylidene group in the present invention, was prepared as described in JP-A-10-30612.
It was produced according to the method of Japanese Patent Publication No. 8 so that the above three types of polybutene correspond to the average molecular weight. As an example, a method for producing the C ₄ olefin polymer having a high concentration terminal vinylidene group (average molecular weight 1300) will be described below.

As a feedstock, isobutene-containing C ₄ raffinate having the following composition% by weight (based on the total amount of the mixture) (butadiene extraction residue from ethylene cracker):
It was used. Isobutene: 50.9 Butene-1: 23.2 Cisbutene-2: 2.8 Transbutene-2: 6.4 Isobutane: 5.4 n-Butane: 11.3.

The polymerization reaction was carried out using the following continuous polymerization apparatus. That is, a 2 L internal volume equipped with a variable stirrer, a low-temperature circulation cooling device capable of constant temperature adjustment, a raw material supply port, a complex catalyst supply port, a polymerization temperature indicator, a stationary tank, a deactivation tank and an outlet. The reactor was installed. A flow rate of 2 L / hour, that is, a contact time between the olefin component and the complex catalyst was set to 1 hour in the reactor, and at the same time, a mole between boron trifluoride and diethyl ether (special grade reagent) was used as the complex catalyst. A boron trifluoride diethyl ether complex adjusted to a ratio of 1.00: 1.00 was continuously added at a ratio of 8.27 mmol with respect to the olefin component of the feedstock to maintain the inside of the reactor at -10 ° C. While carrying out the polymerization reaction.

After the reaction, the complex catalyst was washed with a dilute aqueous solution of sodium hydroxide until it was deactivated, and then the organic phase was separated.
From the obtained organic phase, unreacted feed materials and light components having 24 or less carbon atoms were distilled off by vacuum distillation.

The yield of butene polymer obtained from the product remaining after distilling off the light components was calculated. The molecular weight of the butene polymer was determined by gel permeation chromatography (GPC).
The olefin structure assignment and quantification at the terminal of the molecule was calculated by measuring with a nuclear magnetic resonance apparatus (NMR).

As a result of each analysis, the yield of butene polymer was 49%, the average molecular weight was 1300, and the content of C ₄ olefin polymer containing terminal vinylidene group was 85 mol%.
It was confirmed that a C ₄ olefin polymer having a high concentration of a C ₄ olefin polymer containing a terminal vinylidene group, which is a raw material of an oxygen-containing derivative, having the above properties was obtained.

As the oxygen-containing derivative, an epoxidation reaction product of a terminal vinylidene group was obtained by using peracetic acid according to US Pat. No. 3,382,255. Regarding the addition reaction with a phenol compound, according to JP-A-7-507073, the addition reaction with maleic anhydride is described in the European Polymer Journal of M. Tescher et al., Vol. Two
0, No. 3, 269-280 (1984).

An example of a specific method for producing an oxygen-containing derivative suitable as a sealing material in this example will be described below. Epoxidation reaction : As a synthesizer, a four-necked flask equipped with a variable stirrer, a reaction temperature indicator, a reaction dropping port and a reflux device was installed in a heat medium bath capable of constant temperature control. In this flask, C containing 85 mol% of terminal vinylidene group
₄ C ₄ olefin polymer containing an olefin polymer [average molecular weight (Mn) 1300] to 260 g, heptane 120
40.0 g of 40% peracetic acid solution in the solution so that the reaction temperature becomes 30 ° C or less.
Was added dropwise over 1 hour. After the dropping, the reaction was continued at that temperature for 1 hour.

Next, after separating the aqueous layer portion from the reaction mixture, the organic layer was washed several times with a dilute sodium carbonate solution. The organic layer obtained by the washing was concentrated under reduced pressure at 100 ° C. by an evaporator to recover the target epoxidized C ₄ olefin polymer.

The degree of progress of epoxidation can be determined by a combination of 13 C-NMR analysis and TLC analysis,
In this case, it was found that 90 mol% or more was epoxidized C ₄ olefin polymer. An example of the structural formula of the oxygen-containing derivative obtained by the epoxidation reaction is shown in Formula (1), but the present invention is not limited to this structural formula.

[0066]

[Chemical 1]

Phenolization reaction : The same synthesizer as that used in the epoxidation reaction was used. 14.3 g of phenol melted in a flask was collected, and boron trifluoride etherate 5.2 as a reaction catalyst was collected in the sample.
ml was added dropwise. Then, a solution prepared by dissolving 100 g of C ₄ olefin polymer (Mn1300) containing 85 mol% C ₄ olefin polymer containing terminal vinylidene groups in 130 ml of hexane is maintained in the flask at 30 ° C. or lower. So that it was dropped.

The reaction mixture was reacted at room temperature for 6 hours, the catalyst was deactivated with a dilute sodium hydroxide solution, and then washing with water was repeated 3 times, and the organic layer at that time was recovered.
The organic layer thus obtained was concentrated under reduced pressure at 100 ° C. by an evaporator to obtain a desired phenolized C ₄ olefin polymer.

The degree of progress of this phenolation is 13C-
To be determined by combining NMR analysis and TLC analysis
In this case, 80 mol% or more is phenolized
C _Four It was confirmed to be an olefin polymer.

The C ₄ olefin polymers of Mn650 and Mn2900 were phenolized in the same manner as above. By 13 C-NMR analysis and TLC analysis, it was confirmed that 80 mol% or more of each was a phenolized C ₄ olefin polymer. An example of the structural formula of the oxygen-containing derivative obtained by the phenol reaction is shown in formula (2), but the present invention is not limited to this structural formula.

[0071]

[Chemical 2]

Anisole addition reaction : This addition reaction is
except for using C ₄ olefin polymer n30000 was performed in the same embodiment with the phenol reaction. The degree of progress of this addition reaction can be determined by the combined use of 13 C-NMR analysis and TLC analysis. In this case, it was confirmed that 20 mol% or more was a C ₄ olefin polymer to which anisole was added. . Formula (3) shows an example of the structural formula of the oxygen-containing derivative obtained by the anisole addition reaction, but the present invention is not limited to this structural formula.

[0073]

[Chemical 3]

Maleic anhydride reaction : The same synthesizer as that used in the epoxidation reaction was used. Into the flask, C ₄ olefin polymer containing terminal vinylidene group-containing C ₄ olefin polymer 85 mole% (MN29
00) 100 g and maleic anhydride 7.5 g were sampled, and the temperature was raised to 220 ° C. while mixing and stirring. The reaction was continued at this temperature for 6 hours, and then unreacted maleic anhydride was removed from the reaction product by an evaporator (100 ° C. reduced pressure) to give the target product, maleic anhydride C.
_{A 4} olefin polymer could be obtained.

The degree of progress of this maleic anhydride formation is 13C-
It can be determined by a combination of NMR analysis and TLC analysis, and in this case, 80 mol% or more was found to be a maleic anhydride C ₄ olefin polymer (succinic acid derivative). An example of the structural formula of the oxygen-containing derivative obtained by the maleic anhydride reaction is shown in formula (4), but the present invention is not limited to this structural formula.

[0076]

[Chemical 4]

Succinic acid dimethyl ester addition reaction : This addition reaction can be obtained by dimethyl esterifying a maleic anhydride C ₄ olefin polymer (succinic acid derivative). In the flask, 1 mol of the succinic acid derivative was dissolved in hexane, 0.05 mol of boron trifluoride etherate as a reaction catalyst and 10 mol of methanol were added to the solution, and the mixture was reacted at a reflux temperature for 3 hours. After the reaction, the catalyst was deactivated with a dilute sodium hydroxide solution, and then washing with water was repeated 3 times, and the organic layer at that time was collected. The obtained organic layer was dried by an evaporator to 100
By subjecting the mixture to vacuum concentration at 0 ° C., a target C ₄ olefin polymer in which the succinic acid derivative was dimethyl esterified could be obtained.

The degree of progress of this dimethyl esterification is 1
It can be determined by a combination of 3 C-NMR analysis and TLC analysis, in which case it was found to be a nearly quantitatively dimethyl esterified C ₄ olefin polymer. An example of the structural formula of the oxygen-containing derivative obtained by the succinic acid dimethyl esterification reaction is shown in formula (5), but the present invention is not limited to this structural formula.

[0079]

[Chemical 5]

The oxygen-containing derivative thus obtained,
And iso -C ₄ olefin polymer, were mixed in a molar ratio shown in Table, and the sealing material. Mol% is 13C-NM
Determined by a combination of R and TLC analysis.

The conventional sealant composition containing the comparative C ₄ olefin polymer and the mineral oil diluent in the ratio shown in the table, and the sealant and the diluent thus obtained are shown in the table. With respect to the sealing material composition of the present invention which is included in the ratio of, the performance was evaluated by conducting the following tests.

All Sp value units in the table are (MPa) ^1/2
Is. In addition, in Examples 1 to 3 and Examples 8 to 12, when the sealing material and the diluent were mixed, they became uniform.

EPDM rubber swellability of sealant composition
Evaluation test (based on “oil resistance test” of JIS K 6301) (1) Test piece: EPDM test piece A: width 20 mm × length 50 mm × thickness 2
mm [manufactured by Japan Test Panel Co., Ltd. (manufacturer: Irumagawa Rubber Co., Ltd.)] EPDM test piece B: width about 20 mm x length about 50 mm x thickness about 2 mm [cutout product from weather strip in market distribution] (2 ) Test method: Put a sealing material and a diluent in a beaker so that the compounding ratio shown in the table is obtained, mix and stir them sufficiently to obtain a liquid for a sealing material composition, and then adjust the temperature of this liquid. The equipment was kept at 70 ° C. Subsequently, two kinds of EPDM test pieces (various test times n = 3 times) of which volume and weight were measured were dipped in the sealant composition liquid,
After the lapse of 24 hours, the test piece was taken out, and after wiping the test piece with hexane, the volume and weight of the test piece were measured again to obtain the weight change rate and the volume change rate before and after the immersion.

(3) Evaluation Method The evaluation was performed in the following four stages by calculating the average value of the weight change rate and the volume change rate of the two EPDM test piece total 6 samples.

⊚: Less than + 2%, ○: + 2% or more to +4
%, Δ: + 4% or more to less than + 6%, x: + 6% or more (4) Described in the result table.

Odor test of sealing material composition (1) Test object In the swelling evaluation test, EPD at 70 ° C. for 24 hours
The test was performed on the odor of the liquid for the sealing material composition after the M test piece was dipped. (2) Evaluation method 10 judges evaluated the odor according to the following 4 grades, and the majority opinion was used as a result. ⊚: Almost odorless, ◯: There is a slight odor but not unpleasant, Δ: There is a slight odor and is unpleasant, ×: Strong odor is unpleasant. (3) The results are shown in the table.

Dissolution property to cleaning liquid (1) Test object: A sealing material and a diluent were placed in a beaker so that the mixing ratio shown in the table was obtained, and these were sufficiently mixed and stirred to prepare a liquid for a sealing material composition. Obtained. (2) Evaluation method Methanol in the same weight as the liquid for the sealing material composition was added to the above liquid, the mixture was sufficiently mixed and stirred, and then allowed to stand to observe whether or not phase separation occurred. The reason for the easy phase separation is that it has a low affinity for methanol (the main component of the detergent), so it was judged that the elution to the detergent was also low. The evaluation was performed in the following four stages. ⊚: Phase separation is extremely easy, ◯: Phase separation is performed, Δ: Phase separation is performed, but the interface is unclear, ×: Phase separation is not performed (3) As shown in the result table.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

As described above, the sealant composition containing the oxygen-containing derivative of the C ₄ olefin polymer having a terminal vinylidene group and the oxygen-containing diluent has the same average molecular weight of C ₄
Compared with a conventional sealing material composition containing an olefin polymer and a mineral oil diluent, a swelling suppressing effect of a weather strip required in combination with a weather strip,
It can be seen that the odor control effect and the elution control effect of the weather strip cleaning solution are excellent.

By suppressing the swelling of the weather strip and the elution of the weather strip with the cleaning liquid, it is possible to prevent the weather strip from being deformed to form a gap between the weather strip and the vehicle / building. , Air tightness, vibration control of windows, etc., and rainwater inflow prevention are improved.

Therefore, the sealing material composition of the present invention is
It can be seen that it is particularly suitable for a weatherstrip used for a window frame of a vehicle, a house, etc., which requires good sound insulation, airtightness, vibration suppression of windows and the like, and rainwater inflow prevention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Adachi             39 Toa at 126, 11 Makishima-cho, Uji City, Kyoto Prefecture             Kasei Co., Ltd. F term (reference) 3D201 AA06 CA02 CA17 CB01 EA07A                 4H017 AA04 AB17 AC06 AC18 AC19                       AD06 AE03 AE05                 4J002 AE00Y AE05Y BB17W BB18W                       BB20X BB21X ED036 EH046                       EH056 EH086 EH136 GJ02                       GN00                 4J100 AA04Q AA05Q AA06P AA06Q                       BA03H BA03P BA05P BA20H                       BA20P BC43H BC43P BC54H                       BC54P BC55H BC55P CA01                       CA04 CA31 HA61 HB63 HC09                       HC13 HC30 HC36 JA01 JA05

Claims (9)

[Claims] 1. A C ₄ olefin polymer having an average molecular weight of 100 or more and 60,000 or less, an oxygen-containing derivative of a C ₄ olefin polymer having a terminal vinylidene group and an average molecular weight of 100 or more and 60,000 or less, and (MPa) ^1/2 . A sealing material composition for weatherstrip, which comprises an oxygen-containing diluent having a solubility parameter in the range of 15 to 35. 2. A C ₄ olefin polymer and / or C
₄ The average molecular weight of the oxygen-containing derivative of the olefin polymer is 50
It is 0 or more and 3000 or less, The sealing material composition for weather strips of Claim 1 characterized by the above-mentioned. 3. A C ₄ olefin polymer and / or C
_The sealant composition for weatherstrip according to claim 1 or 2, wherein the repeating unit structure of the oxygen-containing derivative of the ₄ olefin polymer is an isobutene structure. 4. The terminal chemical structure of the oxygen-containing derivative of the C ₄ olefin polymer is epoxidized structure, aliphatic alcohol type hydroxyl group-containing structure, aromatic alcohol type hydroxyl group-containing structure, carboxylic acid type structure, maleic anhydride type. The sealing material for weatherstrip according to any one of claims 1 to 3, wherein the sealing material is at least one selected from the group consisting of a structure, an ester derivative type structure of maleic anhydride, and these derivative structures. Composition. 5. The sealing material for a weather strip according to claim 1, wherein the terminal chemical structure of the oxygen-containing derivative of the C ₄ olefin polymer is a phenol compound type structure. Composition. 6. The sealant composition for weatherstrip according to any one of claims 1 to 5, wherein the oxygen-containing diluent is a vegetable oil or fat. 7. The oxygen-containing diluent is a vegetable oil having a hydroxyl group, according to any one of claims 1 to 5.
The sealing material composition for weather strips as described in 1. 8. The oxygen-containing diluent is at least one selected from the group consisting of castor oil, its derivatives, rice oil and corn oil, according to any one of claims 1 to 5. A sealing material composition for a weather strip. 9. The sealant composition for weatherstrip according to claim 1, wherein the oxygen-containing diluent is a vegetable oil containing vitamin Es.