JP2019001884A - Composition for putty, and structure, movable body and railway vehicle using the same - Google Patents

Abstract

To provide a composition for putty capable of adding sufficient adhesiveness and excellent blister inhibition property.SOLUTION: The composition for putty contains [A] unsaturated polyester, [B] a polymerizable unsaturated compound, [C] a polymerization initiator, and [D] a filler, in which the [B] polymerizable unsaturated compound is a compound containing at least one kind group or structure selected from (B1) styrene, and (B2) a glycidyl group, secondary amine and tertiary amine, and an ethylenic unsaturated group. An SP value of the (B2) compound is preferably 8 to 12. The (B2) compound is preferably a least one kind selected from a group consisting of glycidyl methacrylate, N-vinylpyrrolidone and dimethylaminoethyl acrylate.SELECTED DRAWING: None

Description

  The present invention relates to a putty composition, and a structure, a moving body, and a railway vehicle using the composition.

  A putty for repairing irregularities is provided on the metal surface constituting the body of the railway vehicle, and a decorative coating film is formed on the putty.

  Such putty is required to have excellent adhesion to the underlying metal material and coated film so that it will not easily peel off. There has been proposed a composition containing a crosslinking monomer (see, for example, Patent Document 1).

  This composition contains styrene and hydroxyalkyl (meth) acrylate as crosslinking monomers, and is excellent in that it can improve the heat-resistant adhesion between the putty and the galvanized steel sheet.

JP-A-11-61036

  On the other hand, particularly in railway vehicles, it is also required to suppress blisters (blisters) against the putty as described above so as not to impair the beauty.

  However, the conventional putty composition as described above still cannot sufficiently suppress the generation of blisters, and has not achieved both excellent adhesion and blister suppression.

  This invention is made | formed based on the above situations, The objective is to provide the composition for putty which can be provided with sufficient adhesiveness and the outstanding blister suppression property.

The present invention
(1) [A] unsaturated polyester,
[B] polymerizable unsaturated compound,
[C] a polymerization initiator, and [D] a putty composition containing a filler,
[B] The polymerizable unsaturated compound is
(B1) styrene, and (B2) a compound containing at least one group or structure selected from the group consisting of a glycidyl group, a secondary amine and a tertiary amine, and an ethylenically unsaturated group, A composition for putty,
(2) The putty composition according to (1), wherein the SP value of the compound (B2) is 8 or more and 12 or less,
(3) The putty composition according to (1) or (2), wherein the (B2) compound is at least one selected from the group consisting of glycidyl methacrylate, N-vinylpyrrolidone, and dimethylaminoethyl acrylate,
(4) Any one of (1) to (3), wherein the content of the polymerizable unsaturated compound [B] is 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the [A] unsaturated polyester. The composition for putty according to item,
(5) The putty composition according to any one of (1) to (4), wherein the molar ratio of (B1) styrene to the (B2) compound is 10:90 or more and 80:20 or less,
(6) A structure having a putty formed using the putty composition according to any one of (1) to (5),
(7) A mobile body having a putty formed using the putty composition according to any one of (1) to (5), and (8) any one of (1) to (5) The present invention relates to a railway vehicle having a putty formed using the putty composition according to item 1.

In this specification, the “SP value (dissolution parameter)” means a calculated value calculated by the Fedors equation δ2 = ΣE / ΣV. Where δ is the SP value (unit: √ (cal / cm ³ )), E is the evaporation energy, and V is the molar volume. The Fedors method is described in Journal of Japan Adhesion Association, 1986, Vol. 22, page 566.

  The present invention can provide a composition for putty capable of imparting sufficient adhesion and excellent blister suppression. Therefore, the putty composition can be suitably used for a structure that requires high adhesion and good appearance.

<Composition for putty>
The putty composition of the present invention contains [A] an unsaturated polyester, [B] a polymerizable unsaturated compound, [C] a polymerization initiator, and [D] a filler. Moreover, the said composition may contain [E] arbitrary component, unless the effect of this invention is impaired. Thus, since the said composition for putty contains said each component, it can provide sufficient adhesiveness and the outstanding blister suppression property. This is because [B] the polymerizable unsaturated compound has (B1) styrene and (B2) compound, (B1) the hydrophobicity of styrene, and (B2) adhesion due to specific functional groups of the compound In combination, it is presumed that the putty composition imparts excellent adhesion and blister suppression. Hereinafter, each component will be described in detail.

<[A] Unsaturated polyester>
[A] The unsaturated polyester is a main component of the putty obtained. [A] The unsaturated polyester is a polycondensate of an unsaturated dibasic acid and a polyhydric alcohol, or a modification of this polycondensate. In addition, you may use [A] unsaturated polyester individually or in combination of 2 or more types.

  Examples of the unsaturated dibasic acid include unsaturated dicarboxylic acids such as maleic acid and fumaric acid; and acid anhydrides such as succinic anhydride, phthalic anhydride and maleic anhydride.

  Examples of the polyhydric alcohol include ethylene glycol and propylene glycol.

  Examples of modified polycondensates include those obtained by modifying unsaturated polyester chains with epoxy compounds such as glycidyl methacrylate and bisphenol A type epoxy, isocyanate compounds such as toluene diisocyanate and isopropenyl-dimethyl-benzyl isocyanate, etc. Is mentioned.

  [A] Examples of commercially available unsaturated polyesters include Sandoma CN-203, CN-273, 1864G, 1800, CN-703, CN-705, CN-351, CN- 470 (above, manufactured by DIC Material), Iupica 5523, Iupica 7123 (above, manufactured by Iupika Japan), and the like.

<[B] polymerizable unsaturated compound>
[B] The polymerizable unsaturated compound is a component that hardens the putty composition and improves the adhesion to an adjacent layer. [B] The polymerizable unsaturated compound is composed of (B1) styrene and (B2) compound. In addition, you may use (B1) styrene and (B2) compound individually or in combination of 2 or more types, respectively.

[(B1) Styrene]
(B1) Styrene is a component that cures the putty composition together with the (B2) compound described below. Since the composition for putty contains (B1) styrene, quick drying at the time of putty formation can also be expected.

[(B2) Compound]
The (B2) compound is a compound containing at least one group or structure selected from the group consisting of a glycidyl group, a secondary amine and a tertiary amine, and an ethylenically unsaturated group.

  Examples of the compound containing a glycidyl group and an ethylenically unsaturated group include glycidyl acrylate (SP value 9.9), glycidyl methacrylate (SP value 9.8), and the like.

  Examples of the compound containing a secondary amine structure and an ethylenically unsaturated group include (meth) acrylamide monomers such as N-isopropylacrylamide (SP value 10.6), N-vinylacetamide (SP value 10.9). Etc.

  Examples of the compound containing a tertiary amine structure and an ethylenically unsaturated group include (meth) acrylic monomers such as dimethylaminoethyl acrylate (SP value 9.2), N, N-dimethylacrylamide (SP value 10. 6) (meth) acrylamide monomers such as N, N-diethylacrylamide (SP value 10.2), N-vinylpyrrolidone (SP value 11.4), N-vinylcaprolactam (SP value 10.8), N -Acrylylmorpholine (SP value 11.2), acrylonitrile (SP value 11.1), etc. are mentioned.

  Among these, the (B2) compound preferably has an SP value of 8 or more and 12 or less from the viewpoint of improving compatibility with (B1) styrene. Thereby, a uniform composition can be obtained and a uniform putty can be formed as a result.

  Among the compounds described above, the (B2) compound includes (B1) a tertiary amine structure and an ethylenically unsaturated group from the viewpoint of improving compatibility with styrene, improving adhesion with a coating film, and improving blister suppression. It is also preferably a compound containing a group, and more preferably at least one selected from the group consisting of glycidyl methacrylate, N-vinyl pyrrolidone, and dimethylaminoethyl acrylate.

  [B] The lower limit of the content of the polymerizable unsaturated compound is preferably 50 parts by mass and more preferably 70 parts by mass with respect to 100 parts by mass of the [A] unsaturated polyester from the viewpoint of improving curability. On the other hand, the upper limit of the content is preferably 150 parts by weight, and 120 parts by weight with respect to 100 parts by weight of [A] unsaturated polyester, from the viewpoint of improving workability by preventing a significant decrease in viscosity. More preferred. Therefore, the content of the [B] polymerizable unsaturated compound is such that the coating operation can be easily performed and the curability can be effectively improved. On the other hand, it is preferable that it is 50 to 150 mass parts, and 70 to 120 mass parts is more preferable.

  The molar ratio of (B1) styrene to the (B2) compound is preferably 10:90 or more and 80:20 or less, and more preferably 30:70 or more and 70:30 or less. Thus, by making the said molar ratio into the said range, the outstanding adhesiveness, quick-drying at the time of work, and hardening acceleration | stimulation can be aimed at.

<[C] Polymerization initiator>
[C] The polymerization initiator is a component that facilitates initiation of the polymerization reaction. When the putty composition contains a [C] polymerization initiator, curing by heating, radiation irradiation, or the like can be easily started.

  [C] The polymerization initiator can be selected in a wide range depending on the type of [A] unsaturated polyester to be used, the desired pot life, the curing time at temperature, and the like. [C] Examples of the polymerization initiator include a thermal initiator that generates radicals by thermal energy, an ultraviolet initiator that generates radicals by radiation energy, and an electron beam initiator. In addition, you may use a [C] polymerization initiator individually or in combination of 2 or more types.

  Examples of the thermal initiator include organic peroxides such as ketone peroxide, diacyl peroxide, dialkyl peroxide, hydroperoxide, peroxy ester, and peroxy ketal.

  Examples of the ultraviolet initiator include acylphosphine oxide compounds, benzoin ether compounds, benzophenone compounds, acetophenone compounds, and thioxanthone compounds.

  Examples of the electron beam initiator include halogenated alkylbenzenes and disulfide compounds.

  Among these, as the [C] polymerization initiator, from the viewpoint of curability at room temperature and workability, ketone peroxide and hydroperoxide are preferable, hydroperoxide is more preferable, and cumene hydroperoxide is further preferable.

  [C] As content of a polymerization initiator, [A] 0.1 mass part-6 mass parts are preferable with respect to 100 mass parts of unsaturated polyester, 0.5 mass part-4 mass parts are more preferable, 1 part by mass to 3 parts by mass is more preferable. [C] By making content of a polymerization initiator into the said range, a polymerization reaction can be started easily and timely.

  [C] The polymerization initiator may be blended in advance with the putty composition as long as it does not cure, but it is usually blended at the time of use (during curing). It is preferable to blend at the time of use.

<[D] Filler>
[D] The filler is a component that increases the bulk of the putty. In addition, you may use a [D] filler individually or in combination of 2 or more types.

  [D] Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomite, limestone, gypsum, aluminum fine powder, Examples include hollow balloons, alumina, glass powder, aluminum hydroxide cryolite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and those obtained by surface treatment.

  Among these, as the [D] filler, calcium carbonate, aluminum hydroxide, silica, and talc are preferable and talc is more preferable from the viewpoint of providing high workability, strength and economy, and excellent aesthetics.

  [D] The content of the filler is usually 50 parts by mass to 250 parts by mass with respect to 100 parts by mass of the total amount of [A] unsaturated polyester and [B] polymerizable unsaturated compound.

<[E] Optional component>
As long as the effect of the present invention is not impaired, the putty composition has a viscosity modifier such as a curing accelerator, a polymerization inhibitor, a colorant, and a viscosity reducer, a defoaming agent, a silane coupling agent, and an air barrier such as paraffin. An agent, an ultraviolet absorber, a plasticizer, an aggregate, a flame retardant, a stabilizer, a reinforcing material and the like may be contained. In addition, you may use [E] arbitrary components individually or in combination of 2 or more types, respectively. [E] The content of the optional component can be appropriately selected according to the purpose.

  The curing accelerator is a component that increases the hardness and strength of the resin obtained by increasing the speed of the curing reaction. Examples of the curing accelerator include metal soaps, metal chelates, and amines. The curing accelerator may be blended in advance with the putty composition or may be blended immediately before curing.

  Examples of the metal soaps include cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate.

  Examples of the metal chelates include vanadium acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate.

  Examples of the amines include anilines such as aniline, N, N-dimethylaniline, N, N-diethylaniline, N, N-bis (hydroxyethyl) aniline and diethanolaniline; p-toluidine, N, N- Dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, m-toluidine, etc. Toluidines; 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, etc. Aminobenzaldehydes; triethanolamine, diethylenetriamine, pyridine, phenyl Ruhorin, piperidine and the like.

  As content of a hardening accelerator, it is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of total amounts of [A] unsaturated polyester and [B] polymerizable unsaturated compound.

  The polymerization inhibitor is a component that inhibits polymerization. Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 1,4-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4. -Methylphenol etc. are mentioned. As content of a polymerization inhibitor, it is preferable that it is 0.001-0.1 mass part with respect to 100 mass parts of total amounts of [A] unsaturated polyester and [B] polymerizable unsaturated compound.

  The colorant is a component that colors the putty composition into a desired color. Examples of the colorant include inorganic pigments such as titanium white and carbon black; organic pigments such as phthalocyanine blue and quinacridone red.

<Preparation of composition for putty>
The composition for putty of the present invention is a mixture of [A] unsaturated polyester, [B] polymerizable unsaturated compound, [C] polymerization initiator, [D] filler, and [E] optional components at a predetermined ratio. Can be prepared.

<Method of forming putty>
For example, a blend of [A] unsaturated polyester, [B] polymerizable unsaturated compound, [D] filler, and [E] optional component is used, and [C] polymerization initiator is added immediately before curing. The putty composition is prepared by blending with a blend, and after applying the composition on the structure, a cured putty can be obtained through a predetermined atmosphere, temperature and time. The atmosphere is usually air. The temperature may be either room temperature or warming, but is usually performed when the outside air temperature is low, and at room temperature when the outside air temperature is high. The time can be appropriately determined depending on the temperature and the degree of curing. In addition, you may harden in steps, changing the said conditions.

<Structure>
The structure of the present invention has a putty formed using the putty composition. As described above, since the putty composition can provide a putty composition capable of imparting sufficient adhesion and excellent blister suppression properties, adhesion and good appearance can be obtained. It can be suitably used for forming the surface of a structure such as a fixed object or a moving body that is required.

<Moving object>
The mobile body of the present invention has a putty formed using the putty composition. As described above, since the putty composition can provide a putty composition capable of imparting sufficient adhesion and excellent blister suppression properties, adhesion and good appearance can be obtained. It can be suitably used for forming the surface of a moving body such as a required automobile or railway vehicle.

<Railway vehicle>
The railway vehicle of the present invention has a putty formed using the putty composition. As described above, since the putty composition can provide a putty composition capable of imparting sufficient adhesion and excellent blister suppression properties, adhesion and good appearance can be obtained. It can be suitably used to form the surface of railway vehicles such as locomotives and passenger cars that are required.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

<Preparation of composition for putty>
Each component used for preparation of the composition for putty is shown below.

[A] Unsaturated polyester A-1: CN-703 (manufactured by DH Material, solid content about 65%)
A-2: CN-705 (manufactured by DH Material, solid content about 63%)
[B] Polymerizable unsaturated compound (B1) Component B1-1: Styrene (manufactured by Wako Pure Chemical Industries, reagent special grade)
(B2) Component B2-1: N-vinylpyrrolidone (manufactured by Nippon Shokubai, SP value 11.4)
B2-2: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, special reagent grade, SP value 9.8)
B2-3: Dimethylaminoethyl acrylate (manufactured by Tokyo Chemical Industry, SP value 9.2)
B2-4: N-hydroxyethylacrylamide (manufactured by Tokyo Chemical Industry, SP value 14.4)
B2-5: 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai, SP value 12.45)
B2-6: Acrylamide (Wako Pure Chemical Industries, Wako Grade 1, SP value 14.2)
[C] Polymerization initiator C-1: Cumene hydroperoxide (manufactured by NOF Corporation, model number: Park Mill H-80)
C-2: Diacyl peroxide (manufactured by NOF, model number: NIPER BW)
[D] Filler D-1: Talc (manufactured by Nippon Talc, model number: Talc SW, particle size: average 12 μm)
D-2: Talc (manufactured by Nippon Talc, model number: Talc MS, particle size: average 14 μm)
[E] Optional component E-1: Cobalt accelerator (manufactured by DIC, RP-136)
E-2: Amine accelerator (reagent: dimethylaniline)

[Example 1]
[A] (A-1) was used as the unsaturated polyester, and styrene was removed from this (A-1) by distillation so that the solid content was 100%. Next, 100 parts of the obtained (A-1) is 25 parts by mass of (B1-1) as the component (B1), 45 parts by mass of (B2-1) as the component (B2), and (D- 1) 150 parts by mass and [E] 2 parts by mass of (E-1) and 0.5 parts by mass of (E-2) as optional components were blended, and the mixture was stirred for 15 minutes with the high-speed dissolver. Next, 1.5 parts by mass of (C-1) as a polymerization initiator [C] was added to the above stirred mixture and stirred sufficiently to prepare the putty composition of Example 1.

[Examples 2 to 10 and Comparative Examples 1 to 4]
Each putty composition was prepared in the same manner as in Example 1 except that the types and amounts (parts by mass) of the components to be blended were as shown in Table 1.

<Evaluation>
Adhesion and blister suppression were evaluated and the results are shown in Table 2.

[Adhesion]
Each putty composition was applied to an aluminum plate (alloy number: A6N01, size: 70 mm x 150 mm x 0.8 mm) at a thickness of 2 mm and allowed to stand for 24 hours at 25 ° C to obtain a putty board. It was. Next, the obtained putty plate is lightly polished with a # 400 water-resistant paper, and a coating film is formed by spray coating using an acrylic urethane resin-based top coating (manufactured by Kansai Paint, model name: Retan PG80 white base). A painted plate was prepared. Under the present circumstances, it dried at 25 degreeC for 24 hours, and adjusted so that the film thickness of the coating film after drying might be set to 50 micrometers. Next, the coated plate on which the coating film was formed was immersed in warm water at 60 ° C. for 72 hours, then dried at 40 ° C. for 24 hours, and a cross-cut test (conforming to JIS K 5600-5-6) was performed. Went and evaluated adhesion. The evaluation results were evaluated according to JIS K 5600-5-6 and evaluated from 0 to 5.

[Blister suppression]
Using a coated plate produced by the same method as described in the above [Adhesion] section, this was immersed in warm water at 70 ° C. for 100 hours, and then the warm water was lightly wiped and the surface state was observed within 1 hour. . At this time, if no blistering was observed, the blister suppression property was good “A”, if it was slightly recognized, it was judged as “B”, and if it was easily recognized, it was judged as “C”.

  As can be seen from the results in Table 2, in the comparative examples, the blister suppression was poor, whereas in the examples, both the adhesion and the blister suppression were good.

  The present invention can provide a composition for putty capable of imparting sufficient adhesion and excellent blister suppression. Therefore, the putty composition can be suitably used for a structure that requires high adhesion and good appearance.

Claims (8)

[A] unsaturated polyester,
[B] polymerizable unsaturated compound,
[C] a polymerization initiator, and [D] a putty composition containing a filler,
[B] The polymerizable unsaturated compound is
(B1) styrene, and (B2) a compound containing at least one group or structure selected from the group consisting of a glycidyl group, a secondary amine and a tertiary amine, and an ethylenically unsaturated group, Putty composition.   (B2) The composition for putty according to claim 1, wherein the SP value of the compound is 8 or more and 12 or less.   The putty composition according to claim 1 or 2, wherein the compound (B2) is at least one selected from the group consisting of glycidyl methacrylate, N-vinylpyrrolidone, and dimethylaminoethyl acrylate.   The content of [B] polymerizable unsaturated compound is 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of [A] unsaturated polyester. Composition for putty.   The molar ratio of (B1) styrene and (B2) compound is 10:90 or more and 80:20 or less, The composition for putty of any one of Claims 1-4.   The structure which has the putty formed using the composition for putty of any one of Claims 1-5.   The moving body which has the putty formed using the composition for putty of any one of Claims 1-5.   A rail vehicle having a putty formed using the putty composition according to any one of claims 1 to 5.