JPS60229980A - Vinyl chloride sol sealer - Google Patents

Abstract

PURPOSE:The titled sealer that contains a vinyl chloride resin or its copolymer as a base resin, a temperature-sensitive thixotropic agent and thermally expandable particles, thus showing good inflowing properties and sealing ability, because it has specific flowing properties and thermal expansion. CONSTITUTION:(A) A vinyl chloride or its copolymer is used as a base resin, which is mixed with (B) (i) a temperature-sensitive thixotropic agent of hydrogenated linseed or castor oil and (ii) thermally expandable particles to give the objective thermally setting type sealer. The sealer has horizontal and vertical flowability of less than 10mm. at room temperature for 30min and more than 10mm. at 110 deg.C for 30min. Further, the expansion of the sealer is less than 50% at 110 deg.C for 10min and more than 50% at 140 deg.C for 30min. The flowability of the sealer is preferably more than 50mm. in the horizontal direction and more than 100mm. in the vertical direction at 110 deg.C for 30min and the thermal expansion is preferably more than 80% at 140 deg.C for 30min.

Description

[Detailed description of the invention] [Technical field and conventional technology] The present invention relates to improvements in vinyl chloride sol sheep.

PVC sol sheep is used for spot welding joints in vehicles. As such vinyl chloride sol sheets, there are known ones that have flow properties, those that have almost no flow properties, and those that have thermal foaming properties, depending on the location where they are applied. A vinyl chloride sol sheep having a thermal expansion property is known in JP-A-57-180678, and a thermally expandable one is known in JP-A-55-92779.

[Purpose of the invention]

゛The present invention aims to provide an innovative PVC sol sheet that has both heat flow properties and heat foaming properties, and has excellent resealer inflow properties and sealing properties by adjusting the heat flow properties and heat foaming properties. The purpose is

(Summary of the Invention) The salt pisol sealer of the present invention is a heat-curable sheet containing at least a vinyl chloride resin or a copolymer thereof as a base resin, a temperature-sensitive titanium property imparting agent, and thermally expandable particles; The flow properties at room temperature for 30 minutes are 1011 or less both horizontally and vertically, and the flow properties at 110°C for 30 minutes are 101!1Il1 or more both horizontally and vertically, and the thermal expansion property of the sheet is 110°C 10 less than 50% in minutes,
It is characterized by being 50% or more at 140°C for 30 minutes.

The PVC sol sheep of the present invention hardly flows at room temperature,
It has great fluidity at about 110°C. On the other hand, the thermal expansibility is low at about 110°C, and large at about 140°C. For this reason, heating first generates fluidity, which allows it to penetrate into a predetermined sealing area, and then expands to ensure a secure seal.

[Detailed explanation of the structure of the invention]

The main components of the vinyl chloride sol sheep of the present invention are a base resin, a temperature-sensitive titanium property imparting agent, and thermally expandable particles.

The base resin is a vinyl chloride resin or a copolymer resin with vinyl chloride, and usually has an average degree of polymerization of about 500 to 3,000. When the total sheep is 100jl% (the same applies below), the base resin content is 5 to 50% by weight,
More preferably, it is 15 to 30% by weight.

The temperature-sensitive titanium properties imparting agent imparts flow properties to the sheep at high temperatures, and refers to hydrogenated oils such as hydrogenated linseed oil and hydrogenated castor oil, and thermoplastic resins such as low-humidity melting polyethylene. These temperature-sensitive titanium properties imparting agents can be blended alone into the base resin, or a plurality of titanium properties imparting agents may be used in combination. The blending ratio of temperature-sensitive titanium property imparting agent is 0.
．． The amount is 1 to 10 parts by weight, more preferably 0.51 to 30% by weight.

Thermally expandable particles are thermally expandable, thermoplastic polymer particles containing a volatile fluid blowing agent, such as those described in JP-A-41-26524. These thermally expandable particles expand when the volatile fluid is gasified by heating, and at the same time, the capsule-shaped thermoplastic polymer containing the volatile fluid softens.
It expands due to gas pressure. Various types of thermally expandable particles are known that can foam at any temperature depending on the boiling point of the volatile fluid contained therein.

In the present invention, it is heated to 110°C 1 when mixed in PVC sol sheep.
Expansion of 50% or less in 0 minutes, 50% in 30 minutes at 140℃
% or more of thermally expandable particles are employed. The blending ratio of thermally expandable particles is about 1 to 10% by weight. More preferably, it is 3 to 7% by weight.

The PVC sol sheep of the present invention may contain calcium carbonate, talc, zincate, titanium oxide, clay, kaolin, silica, etc.
A filler such as alumina can be used in a proportion of 20 to 6011 I%.

As a plasticizer, heptatarate esters such as oop and o top are preferable, and DOA, BPBG, Doz, oos
Polyester plasticizers such as adipic acid-based, trimellitic acid-based, and phthalic acid-based plasticizers can also be used. These plasticizers can be used in a proportion of 5 to 50% by weight. By using 0.1 to 30 parts by weight of a well-known non-temperature-sensitive titanium property imparting agent as another additive, it is possible to increase or decrease the amount of flow during heating. Known examples of these non-temperature-sensitive titanium-imparting agents include hydrated silicic acid, anhydrous silicic acid, organic bentonite, and ultrafine particles of calcium carbonate. Furthermore, 0.1% of the adhesion imparting agent
~10% by weight can be used. As the adhesion imparting agent, conventionally known ones such as acrylic, amine, imine and the like can be used. Furthermore, when stability of the sheep is required, metal salts such as Pb, 3a, 7n, 3n, Ca, and hygroscopic agents such as Ca2O, Altos, CaCl, etc. can be used as stabilizers.

The salt pisol sealer of the present invention has flow properties of 101 or less both horizontally and vertically at room temperature for 30 minutes, and at 110°C.
The flow properties for 30 minutes are 1Ql1 or more both horizontally and vertically. Note that flowability is defined by JIS K6830.
Based on the fluidity test of -13(2), the test was conducted using a semicircular beat having a diameter of 1011 mm. Both the horizontal and vertical flowability testing methods measure the flow of the kneader when the test plate to which the semicircular beat of the kneader is attached is maintained vertically. In the horizontal test, the semicircular beat of the kneader extends in the horizontal direction, whereas in the vertical test, the semicircular beat extends in the vertical direction. In addition, the flowability of the kneader is 11
It is more preferable that the flow properties at 0° C. for 30 minutes are 5 Qmw or more horizontally and 10011 or more vertically.

The thermal expansion property of the vinyl chloride sol kneader of the present invention is 50% or less at 110°C for 10 minutes, and 50% or more at 140°C for 30 minutes.

More preferably, the thermal expansion at 140°C for 30 minutes is 80%.
That's all. Note that thermal expandability is the value obtained by dividing the volume increased from the volume before expansion by the volume before expansion by 10
It is multiplied by 0. Therefore, thermal expansion of 50% means that the volume is 1.5 times the original volume.

The vinyl chloride sol kneader of the present invention can be obtained by blending the above-described base resin, temperature-sensitive titaso imparting agent, thermally expandable particles, and other ingredients and kneading the mixture in a kneader or the like.

〔Example〕

N001~ shown in Table 1 as the PVC sol kneader of the present invention
A PVC sol kneader of N004 was prepared.

The vinyl chloride resin used here had a polymerization r of 11,000 to 2,000. Further, calcium carbonate was used as a filler, DOP was used as a plasticizer, and hydrogenated castor oil was used as a temperature-sensitive titanium-imparting agent.

Tin was used as a stabilizer. As thermally expandable microcapsules, those having a particle size of 5 to 30 μm and containing isobutane as a volatile fluid were used.

As comparative examples, two types shown in No. 11 and No. 12 were used. Each of these vinyl chloride sol kneaders was obtained by individually kneading in a kneader for 1.5 hours and then degassing and stirring in the kneader for 2 hours.

Next, each kneader obtained was tested using JIS K6830-13 (
A vertical fluidity test was conducted according to 2). The results are also shown in the table. Also, in order to see the thermal expansion property, 11
Using a heating furnace maintained at 0°C, 120°C, 130°C and 140°C, the volume expansion coefficient when inserted at 110°C for 8 minutes, 30 at 120°C, 130°C or 140°C
The volumetric expansion coefficient when the sample was left to stand for 8 minutes at 110°C and then the volumetric expansion coefficient after it was left to stand at 140°C for 30 minutes were measured. The results are shown in Table 2.

As is clear from Table 2, the salt pisol sealer of this example shows almost no flowability at room temperature, but begins to show flowability at temperatures above 110°C.

Note that this flowability is particularly large even at 140℃, and at 110℃ to 140℃.
It shows almost the same flow performance between ℃ and ℃. The volume expansion coefficient is′
50% or less at 110℃ for 10 minutes or more, and 50% or more at 140℃ for 30 minutes or more, the expansion rate is relatively small below 110℃, and the expansion rate is large at a high temperature of 140℃1.
ing·.

On the other hand, Comparative Example No. 11 has almost the same fluidity as the Example, but has no thermal expansion. On the other hand, samples No. 12 are fluid at room temperature.

Next, these salt pizol sealers were applied to the upper part of the sloping door hemming part of an automobile, and the heating in the process was used to heat up the body, and the performance of the PVC sol sealer was investigated. Heating was performed for 10 minutes at 110°C for the first baking, and for 3 minutes at 140°C for the secondary baking.
0 minutes, and 30 minutes at 140°C for tertiary baking.

The PVC sol sheep No. 001 to No. 4 of this example flowed into the sWA of the door hemming part of an automobile during the first baking, and foamed and hardened during the second baking to obtain a reliable seal.

On the other hand, Comparative Example No. 11 PVC sol sheep successfully flowed into the gap in the door hemming part, but lack of sealer was observed in some parts where the width of am was wide. Also No, 1
The salt pisol sealer No. 2 began to flow before it was baked, and it gathered in the low part of the gap in the door hemming area and expanded. This caused a shortage of sheep in the high crevices.

Claims (3)

[Claims] (1) A heat-curable sheet containing at least a vinyl chloride resin or a copolymer thereof as a base resin, a temperature-sensitive thixotropic agent, and thermally expandable particles, the sheet having flow properties at room temperature for 30 minutes. 10111 Ill or less both horizontally and vertically, and the flow properties at 110°C for 30 minutes are 1011 or more both horizontally and vertically, and the thermal expansion of the sheep is 50% or less at 110°C for 10 minutes,
A vinyl chloride sol sheep, characterized in that the temperature is 50% or more at 140°C for 30 minutes. (2) Flow properties at 110℃ for 30 minutes are horizontal and 501
11 or more, vertically 100111 or more, and 140
The vinyl chloride sol sheep according to claim 1, which has a thermal expansion property of 80% or more at 30 minutes at °C. (3) When the whole is bound to 100%, the blending amount of the temperature-sensitive thixotropic agent is 0.1 to 10! The vinyl chloride sol sheep according to claim 1, wherein the amount of thermally expandable particles is 1 to 10% by weight.