JP5159146B2 - Waterproof layer structure - Google Patents

Description

  The present invention relates to a waterproof layer structure excellent in workability such as impregnation and processing in waterproofing materials used in the construction field, particularly in veranda waterproofing applications.

  Fiber reinforced resin constructed for waterproofing is strong and strong in surface strength and durability, and is waterproof with excellent durability and dimensional stability, so it attracts attention as a floor lining method for residential verandas, rooftops, parking lots, etc. Has been. Such waterproof construction forms a fiber reinforced resin layer on a conventionally used waterproof base such as non-combustible board, plywood, calcium silicate board, mortar, concrete, etc., and weather resistance, smoothness on the fiber reinforced resin layer. It is carried out by providing a topcoat resin layer for the purpose of improving property and aesthetics and protecting the fiber reinforced resin layer.

  A resin composition comprising a urethane acrylate resin and a polymerizable unsaturated monomer is cured into a sheet shape, and the tensile elongation at 0 ° C. is 20% or more in a tensile test specified by JIS K-6301. A flexible sheet, a manufacturing method thereof, a waterproof and anticorrosive material using the same, and a waterproof and anticorrosive structure using the same are highly flexible even at low temperature using a thermosetting resin, and water resistant It is disclosed that it is a waterproof and anticorrosive structure having excellent properties and chemical resistance. (Patent Document 1)

  The on-site construction FRP lining method characterized by lining FRP made of vinylon chopped strand mat and plastic on the base material at the site does not cause scattering / diffusion like glass mats, water tightness, reinforcement effect It is disclosed that it is excellent in alkali resistance, finish, workability, workability and the like. (Patent Document 2)

  A composition of 20:70 to 80:10, in which the unfolded staple fiber group having a fiber length of 25 to 150 mm and a non-crimped staple fiber group in which a plurality of fibers exist in a converged state is 20:70 to 80:10 The fibers are mixed in a ratio, and the fibers are bonded by adhesive fibers having crimps, and at least 30% by weight of the total fibers are fibers without crimps, and the adhesive fibers having crimps are all configured. It is disclosed that a non-glass-based reinforcing sheet material characterized by 2 to 50% by weight of fibers has good permeability and excellent strength. (Patent Document 3)

  In the glass fiber chopped strand mat, the glass fiber is likely to be scattered and diffused, and there is a risk of adverse health effects on workers on site construction. Further, it was not easy to clean the scattered and diffused glass mat. Further, in the non-glass fiber mat, there was no environmental problem in the work that occurs in the glass fiber chopped strand mat, but when they were overlapped, unevenness was produced in the finish and a water pool was generated. Moreover, when it processed by butt | matching, the malfunction that intensity | strength was not acquired was produced in the butt | matching part.

  On the other hand, in a general radical curable resin composition containing an unsaturated polyester resin, it is generally unnecessary to use a solvent, but the monomer used in combination with the resin also serves as the solvent. In recent years, high volatility monomers such as styrene and methyl methacrylate have been increasingly used in society to regulate their use due to problems such as volatility and odor. A radical curable resin using few monomers is disclosed. (Patent Documents 4 and 5)

JP-A-10-217414 JP 2000-84482 A JP 63-42952 JP 2003-268054 A JP 2005-054068 A

  Although the FRP waterproof coating film formed of radically polymerizable resin is tough, its resistance to strain is inferior, and there is a problem that cracks are likely to occur at the entrance and exit corners and joints of the base material. .

  The problem to be solved is to obtain a waterproof layer structure that does not deteriorate the working environment due to glass fibers, can secure a joint state similar to that of a glass fiber reinforced reinforced waterproof structure, and is excellent in resistance to strain.

The invention of claim 1 includes a coating material containing a room temperature-curing radically polymerizable resin, a mat-like fiber reinforced fabric containing 30 to 70% by weight of vinylon chopped strands and 10 to 20% by weight of thermally adhesive fibers. , A waterproof structure characterized in that the tensile product of the impregnated and compounded fiber reinforced waterproof layer is 50 to 150 N / mm, there is no scattering of glass fiber, it has excellent resistance to strain and is durable, Similar to the glass fiber chopped strand mat, there is little unevenness at the joint between the mats.

The invention according to claim 2 is the waterproof structure according to claim 1, wherein the radical polymerizable resin having a molecular weight of 180 to 500 is a low odor radical polymerizable resin. Of volatile organic components will not dissipate.

The invention of claim 3 is a mat-like fiber comprising a coating material containing a room-temperature-curing radical polymerizable resin, 30 to 70% by weight vinylon chopped strands and 10 to 20% by weight of heat-adhesive fibers on the base substrate. A construction method for forming a waterproof structure of a fiber reinforced waterproof layer having a tensile strength product of 50 to 150 N / mm, which is impregnated with a reinforcing cloth, and is capable of constructing a strong waterproof layer without leakage it can. After the above construction, an overcoat layer (topcoat layer) may be provided in order to improve the waterproof layer protection, durability, and aesthetics.

The invention of claim 3 is a mat-like fiber reinforcement comprising a coating material containing a room temperature curing radical polymerizable resin on a base substrate, 30 to 70% by weight of vinylon chopped strands and 10 to 20% by weight of thermally adhesive fibers. A construction method for forming a waterproof structure of a fiber reinforced waterproof layer having a tensile strength product of 50 to 150 N / mm, which is impregnated with a cloth, and a tough waterproof layer without leakage can be applied. . After the above construction, an overcoat layer (topcoat layer) may be provided in order to improve the waterproof layer protection, durability, and aesthetics.

Invention of Claim 4 is the construction method of the waterproof structure of Claim 3 , wherein the radical polymerizable resin is a low odor radical polymerizable resin having a molecular weight of 180 to 500 , Volatile organic components such as styrene are not released from the waterproof layer.

  A mat mainly composed of vinylon chopped strands and thermally adhesive fibers is hereinafter abbreviated as a vinylon fiber mat.

  According to the present invention, in the waterproofing of the veranda, the jointing state between the reinforcing fabrics is the same as that of the glass fiber chopped strand mat, there is no scattering or diffusion of the glass fibers, and there is no adverse health effect on the workers on site construction. It will be easy to clean up. The waterproof layer structure does not break or crack and has high strain resistance.

  The waterproof structure of the present invention comprises a non-combustible plate, plywood, calcium silicate plate, mortar, concrete, etc. with a waterproof layer, and does not use a glass fiber chopped strand mat, and has a finish similar to this, Strength is obtained.

  If the fiber reinforced fabric is merely abutted, a weak point is generated there, so that the fiber reinforced fabric is overlapped in the range of 30 to 65 mm. However, the overlapping causes swelling in this portion, resulting in poor finish and a liquid pool. In order to avoid this, fibers are distributed evenly by unraveling or tearing the ends of the reinforcing fabric.

Vinylon Fiber Mat In the vinylon fiber mat used in the present invention, the vinylon chopped strand is a group of unopened staple fibers without crimps in which a plurality of fibers of Patent Document 3 are present in a converged state. It depends on the adhesive fibers. The heat-fusible fiber may be a fiber made of a single resin, or a composite-type heat-fusible fiber such as a side-by-side type or a core-sheath type made of two or more resin components having different melting points. Also good. Composite-type heat-fusible fibers are preferred in order to lower the processing temperature, increase the bondability, and maintain the strength properties. Moreover, an adhesive polyester fiber is preferable from the viewpoint of adhesiveness with vinylon fibers and adhesiveness with the resin to be impregnated. The ratio of the heat-fusible fiber to the entire mat is preferably 10 to 20% by weight. When it is 10% by weight or more, it is excellent in handling property, and a person can work on it during the work, and the fiber is detached by the handling with the roller so that the workability is not lowered by winding around the roller. If it is 20% by weight or less, the permeability of the resin is not hindered, the dispersion of the mat and the bulk density are small at the time of heat-sealing, and the cost of the mat is not increased.

  The strength of the waterproof structure depends on the ratio of the chopped strands in the whole, and also depends on the number of converged fibers and the fiber diameter, but the ratio of the chopped strands is 30 to 70% by weight, so that both permeability and strength can be achieved. Moreover, the manufacturing method of a mat | matte has a wet type and a dry type, A several web is piled up and thermocompression-bonded, and the target basic weight and specification are obtained. Suitable methods for handling the roller during construction include increasing the hot pressure condition, distributing a large amount of heat-fusible fibers on the surface, and applying a resin to the surface. Examples of such vinylon fiber mat products include VM-110WL and VM-135WL of Nippon Vilene Co., Ltd., and JR-200 of Aika Industry Co., Ltd.

Room Temperature Curing Radical Polymerization Resin Room Temperature Curing Radical Polymerization Resin refers to a resin that is polymerized and cross-linked at room temperature using a radical polymerization resin such as unsaturated polyester resin, vinyl ester resin, and acrylic resin in combination with a radical polymerization catalyst and an accelerator. . The coating material is blended with an additive that functions as a coating material such as a thixotropic agent, a filler, and a viscosity modifier.

The unsaturated polyester resin has a double bond titer of 300 to 1800, and preferably contains a polymerizable monomer and an alicyclic amine. When the double bond titer is 300 or more, the fatigue resistance of the fiber reinforced resin layer is improved, and the followability to the base is improved. When the double bond titer is 1800 or less, the fiber reinforced resin layer serving as a waterproof layer is excellent in strength and surface hardness.
The double bond titer is the number of mass (g) of unsaturated polyester resin per mol of polymerizable double bond, and is calculated by, for example, the following formula (formula 1); (double bond titer) = [(Acid component + glycol component) -condensed water] / mol number of unsaturated acid.
The unsaturated polyester resin is composed of an unsaturated alkyd and a polymerizable monomer.

Low odor radical polymerizable resin Low odor radical polymerizable resin is composed of a resin having a polymerizable unsaturated group and a monomer. Examples of the resin having a polymerizable unsaturated group include vinyl esters, that is, epoxy (meth) acrylates. , Urethane (meth) acrylate, polyester (meth) acrylate, and the like. These may be used alone or in combination of two or more depending on the application. Monomers have low volatility, and a molecular weight of 180 to 500 is preferable in terms of volatility and suppression of odor. Specific examples include phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenol ethylene oxide-modified acrylate, nonylphenyl carbitol acrylate, and the like. Two or more kinds may be used in combination. Specific examples of the low odor radical polymerizable resin composition include Aika Jolieths JE-2008 (trade name) manufactured by Aika Industry Co., Ltd., and Polylite HFR-370 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. S-2NS, S-3NS, etc. of Sowa Chemical Industry Co., Ltd.

  Furthermore, alicyclic amines can be used for the purpose of capturing formaldehyde, which is one cause of sick house syndrome. As the alicyclic amine, one or more types such as morpholine, piperidine, piperazine, pyrrolidine and the like are suitable for use. In addition, the alicyclic amine used in the present invention includes an amine compound formed by reacting a pre-prepared product with a resin skeleton or other compound in the resin composition. In order to sufficiently suppress the amount of formaldehyde emitted, a room-temperature-curing radical polymerizable resin: alicyclic amine of 100: 0.01 to 3.0 (weight ratio) is suitable. The amount is preferably 1.8 mg / L or less.

Construction method Specifically, a primer is applied on the base substrate such as non-combustible board, plywood, calcium silicate board, mortar, concrete, etc., if primer is applied, after primer drying, vinylon fiber mat and A fiber reinforced waterproof layer is formed using a polymerizable resin as an essential constituent material, and a top coat layer is provided on the fiber reinforced waterproof layer as necessary.

More specifically, in the treatment process of the waterproof base substrate, in order to improve the adhesion between the base substrate and the fiber-reinforced waterproof layer, it is preferable to remove dirt, deposits, or a fragile surface layer, for example, Clean and clean the surface with shot blasting, sandpaper, etc. Further, in order to improve the adhesion, 0.1 to 0.2 kg / m ² of a polyurethane resin-based, unsaturated polyester-based, vinyl ester resin-based, acrylic resin-based, or urethane acrylate resin-based primer may be applied. .

After drying the primer, lay a fiber reinforced waterproof layer. The fiber-reinforced waterproof layer is formed in a state where a vinylon fiber mat and a polymerizable resin are combined. The vinylon fiber mat preferably has a total basis weight used of 60 to 300 g / m ² according to required quality such as required coating thickness and impregnation.

A polymerizable resin coating material suitable for forming a fiber-reinforced waterproof layer in combination with this vinylon fiber mat is a cast product prepared in accordance with JIS K 6919: 1992 (plastic tensile test method) at 40 ° C. at 24 ° C. About what was hardened | cured after time-hardening, the thing whose tensile strength measured according to JISK6251: 1993 (tensile test method of vulcanized rubber) is 10-50 Mpa and tensile breaking elongation is 20-120% is preferable. When the tensile strength is 10 MPa or more, or the tensile elongation at break is 120% or less, the waterproof structure is excellent in water resistance, surface hardness, durability, etc., and the tensile strength is 50 MPa or less, or the tensile elongation at break is 20% or more. And even if it is a wooden base material, it follows and a crack does not generate | occur | produce.
The viscosity of the polymerizable resin coating material is such that the viscosity at 25 ° C. measured using a BM type rotational viscometer (No. 3 or No. 4, 60 rpm) is in the range of 0.15 to 1.5 Pa · s. Those are preferred. If the viscosity falls outside this range, uniform coating with the applicator cannot be performed smoothly if the viscosity is less than the lower limit. If the waterproof base is uneven, a portion of the coating material that is not filled with resin is generated. In addition, when the upper limit is exceeded, the permeability is poor, and the load on the operation of the applicator is high, resulting in poor workability.

It is preferable that the vinylon fiber mat has 1 to 3 layers, the coating amount of the polymerizable resin coating material is 1.0 to 5.0 kg / m ² , and the fiber reinforced waterproof layer is formed. It is determined according to required performance such as construction period and impact resistance.

In addition, it is possible to apply 0.2 to 2.0 kg / m ² of a soft resin in order to alleviate movements such as dimensional change of the base after drying the primer. Examples of the soft resin include unsaturated polyester resins, polyurethane resins, acrylic resins, and urethanes having a tensile elongation at break of 30 to 300% measured according to JIS A6021: 2000 (waterproofing material for architectural coatings). Acrylate resins are suitable for use. When this step is performed, the above-described fiber-reinforced waterproof layer is formed after the soft resin is cured.

In addition, after forming the fiber reinforced waterproof layer, 0.2 to 2.0 kg of the same room temperature curing radical polymerizable resin coating material used for the fiber reinforced waterproof layer mainly for further improving the finish of the top coat layer. / M ² can also be applied.

After forming the fiber reinforced waterproof layer, it is preferable to provide a topcoat layer in order to protect the fiber reinforced waterproof layer and improve durability and aesthetics. As the resin composition used for the top coat layer, the same resin-based coating material is preferably used when the polymerizable resin coating material is an unsaturated polyester resin. Specifically, it is Jolies JE-2080 (manufactured by Aika Kogyo Co., Ltd., trade name), and the coating amount is preferably 0.2 to 0.6 kg / m ² , but the drying time, Select according to the required performance such as impact.

  Furthermore, a low odor radical polymerizable resin coating material or a water-based acrylic resin coating material can also be used from an environmental viewpoint. Specifically, Joliath JE-2008 (product name) manufactured by Aika Kogyo Co., Ltd. is used as the former, NP-202NS top (product name manufactured by Nippo Chemical Industry Co., Ltd.), and Joliase JA-180 (product name is used as the latter). Aika Kogyo Co., Ltd., trade name).

The product of tensile strength and elongation as a layer of the tensile product waterproof structure is a tensile product, and can be an index that does not cause waterproof destruction, and 50 to 150 N / mm can be achieved by using a vinylon fiber mat. It is an effective index under the premise of a large stress that resists strain, and the crow fiber reinforced one is smaller than the vinylon fiber mat reinforced, and the vinylon fiber mat reinforced has high resistance to strain.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to these examples.

After applying 0.2 kg / m ² of solvent-type urethane resin primer (manufactured by Aika Kogyo Co., Ltd., JU-1270) on the plywood substrate, drying, Jolieth JE-2006 (manufactured by Aika Kogyo Co., Ltd., unsaturated polyester resin) , Trade name) 0.5 kg / m ² applied, vinylon fiber mat JR-200 (manufactured by Aika Kogyo Co., Ltd., basis weight 0.14 kg / m ² , trade name) is laid on top, and JE-2006 Was applied at 1.0 kg / m ^2, and a fiber-reinforced waterproof layer was laid. After the fiber-reinforced waterproof layer was cured, JE-2006 was further applied at 0.5 kg / m ² . After curing, 0.4 kg / m ² of Jolieth JE-2080 was applied as a top coat layer. Note that mat joining was performed by loosening the ends. The wrap width was 50 mm.

Example 2 was carried out in the same manner except that Polylite HFR-370 was used instead of JE-2006 of Example 1 and Jolie's JA-180 was used instead of Jolie's JE-2080. This method was highly environmentally friendly without using styrene or a solvent.

Comparative Example 1
Instead of the vinylon fiber mat of Example 1, JR-98KM (Aika Industry Co., Ltd., glass fiber chopped strand mat, weight per unit area: 0.45 kg / m ² ) was used. Comparative Example 1 was carried out in the same manner as in Example 1 except that the amount was changed from 0 kg / m ² to 0.8 kg / m ² .

Comparative Example 2
Instead of the vinylon fiber mat of Example 1, Frekipe S (Mitsui Chemicals Co., Ltd., acrylic fiber nonwoven fabric, basis weight 0.10 kg / m ² ) was used, and 1.0 kg of Jolie's JE-2006 applied thereafter. Comparative Example 2 was carried out in the same manner as in Example 1 except that the pressure was changed from 0.6 m / m ² to 0.6 kg / m ² .

Comparative Example 3
Comparative Example 3 was carried out in the same manner as Example 1 except that Spunbond 4131N (Toyobo Co., Ltd., polyester fiber nonwoven fabric, basis weight 0.13 kg / m ² , trade name) was used instead of the vinylon fiber mat of Example 1. . In addition, the end of the wrap portion could not be unraveled, and the wrap was performed without unraveling.

Comparative Example 4
Instead of the vinylon fiber mat of Example 2, JR-98 (Aika Kogyo Co., Ltd., glass chopped strand mat, weight per unit area: 0.45 kg / m ² ) was applied, and then Polylite HFR-370 (Dainippon Ink Chemical Co., Ltd.) was applied. Comparative Example 4 was carried out in the same manner as in Example 2 except that the trade name, manufactured by Kogyo Co., Ltd., was changed from 1.0 kg / m ² to 0.8 kg / m ² .

Comparative Example 5
Instead of the vinylon fiber mat of Example 2, Frekipe S (Mitsui Chemicals Co., Ltd., acrylic fiber nonwoven fabric, basis weight 0.10 kg / m ² , trade name) was used, and then Polylite HFR-370 applied was 1 Comparative Example 5 was carried out in the same manner as in Example 2 except that the amount was changed from 0.0 kg / m ² to 0.6 kg / m ² .

Comparative Example 6
Comparative Example 6 was made in the same manner as in Example 1, except that spunbond 4131N was used instead of the vinylon fiber mat of Example 2. In addition, the end of the wrap portion could not be unraveled, and the wrap was performed without unraveling.

Comparative Example 7
Comparative Example 7 was made in the same manner as Comparative Example 3 except that the wrap width was eliminated and the butt was made. The results are the same as in Comparative Example 3 except for the joint portion, the thickness of the joint portion is 1.6 mm, the thickness increase rate is −3%, the tensile strength of the joint portion is 15.4 MPa elongation 26%, The tensile product was 80 N / mm.

Impregnation test The impregnation test was conducted in an atmosphere of 23 ° C. and a relative humidity of 60%.
As a base, a plate glass having a size of 150 × 150 mm with a diagonal line drawn was used. A mat test piece cut to a size of 100 x 100 mm is placed in the center, and about 20 g of room temperature curing radical polymerizable resin without a curing agent is dripped from a height of about 20 cm, and then the diagonal line on the back surface (glass surface) is clear The time until it can be visually confirmed was measured. The evaluation results were classified and evaluated as follows.
○: Less than 15 seconds Δ: 15 seconds or more and less than 30 seconds ×: 30 seconds or more

Wrap part finish test method 1) Preparation of test piece Prepare two pieces each cut into a dimension of 175 x 300 mm so that the lap width of the fiber mat is about 50 mm, and have an inner dimension of about 300 x 300 x 2 mm. It was spread on a mold, impregnated with a polymerizable resin coating material, and cured. The wrap side end portion having a dimension of about 175 × 300 mm was prepared by reducing the amount of fiber mat end area per unit area (ear loosening treatment).
2) Measurement of the thickness of the lap part Measure the coating film thickness of the lap part and non-wrap part of the test piece prepared in 1) using calipers (accuracy 0.05 mm), excluding the maximum and minimum values. The average value at three locations was recorded as the thickness of the formed coating film. The lap thickness increase rate was calculated by the following formula.
(Lap thickness increase rate,%) = (Δt / t) × 100
Here, Δt: (film thickness of the wrap portion) − (film thickness other than the wrap portion) [mm]
t: thickness of coating film other than lapping part [mm]
The evaluation results were classified and evaluated as follows.
○: Lap thickness increase rate less than 25% △: Lap thickness increase rate 25% or more and less than 60% X: Lap thickness increase rate 60% or more

Tensile Strength (N / mm ² ), Elongation (%) and Tensile Product (N / mm) Test I) Production of Tensile Strength Test Specimen Tensile strength test specimens conform to JIS A6021. It was produced under the conditions of Examples and Comparative Examples (no primer), and dumbbell-shaped No. 2 test pieces were used, which were left standing at 23 ± 2 ° C. and relative humidity 60% for 168 hours, respectively.
II) Tensile strength test According to JIS A6021, the tensile strength test of the specimen prepared in I) was performed using a universal testing machine, and the tensile strength, elongation rate, and tensile product were calculated.

Strain resistance I) Preparation of test specimen for bending strength test It was prepared in accordance with JIS A6021 under the conditions of Examples and Comparative Examples (no primer), and was a strip of about 30 x 120 x (each thickness) mm. Samples were prepared and allowed to stand for 168 hours at 23 ± 2 ° C. and 60% relative humidity, respectively.
II) Bending strength test Using an Instron universal testing machine, the bending strength test of the specimen prepared in I) was conducted by the centralized loading method with a gauge distance of 30 mm, and the strain resistance was evaluated. First, the bending load was loaded, the displacement at the yield point where the maximum stress was reached was recorded, and the condition of the waterproof layer of the test specimen at that time was classified and evaluated as follows.
○: There is no abnormality in the specimen. △: There is a slight break or crack that does not penetrate the specimen. ×: There is a break or crack that penetrates the specimen.

Alkali Resistance Test According to JIS A6021, the tensile strength test was performed on the test specimen after the alkali deterioration treatment, and the tensile strength retention rate and elongation retention rate were calculated.
The evaluation results were classified and evaluated as follows. However, priority is given to the lower order.
○: When tensile strength retention is 80% or more and elongation retention is 100% or more Δ: When tensile strength retention is 70% or more and less than 80% or elongation retention is 80% or more and less than 100% ×: When the tensile strength retention rate is less than 70% or the elongation retention rate is less than 80%, the construction environment is evaluated as ◯ when the glass fiber is not scattered, and X when the glass fiber is scattered.
Comprehensive evaluation All the impregnation, lap thickness, alkali resistance, and construction environment were marked with ◯, and the others were marked with x.

The right side of the vinylon fiber mats of Examples 1 and 2 is a loosening photograph. The right side of the glass fiber chopped strand mats of Comparative Examples 1 and 4 is a loosening photo. The right side of the acrylic fiber nonwoven fabric mat of Comparative Examples 2 and 5 is a loosening photo. An example of unraveling a vinylon fiber mat (2 webs).

Claims (4)

  A coating material containing a room temperature curing radically polymerizable resin, 30 to 70% by weight of vinylon chopped strands and 10 to 20% by weight of a mat-like fiber reinforced fabric containing thermal adhesive fibers were impregnated and combined. A waterproof structure, wherein a tensile product of the fiber-reinforced waterproof layer is 50 to 150 N / mm.   The waterproof structure according to claim 1, wherein the radical polymerizable resin is a low odor radical polymerizable resin having a molecular weight of 180 to 500. The base substrate is impregnated with a coating material containing a room temperature-curing radical polymerizable resin, a mat-like fiber reinforced fabric containing 30 to 70% by weight of vinylon chopped strands and 10 to 20% by weight of thermally adhesive fibers. A construction method for forming a waterproof structure of a composite, fiber-reinforced waterproof layer having a tensile product of 50 to 150 N / mm.   The method for constructing a waterproof structure according to claim 3, wherein the radical polymerizable resin is a low odor radical polymerizable resin having a molecular weight of 180 to 500.