WO2017188283A1 - Resin foam and composite - Google Patents

Resin foam and composite Download PDF

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Publication number
WO2017188283A1
WO2017188283A1 PCT/JP2017/016440 JP2017016440W WO2017188283A1 WO 2017188283 A1 WO2017188283 A1 WO 2017188283A1 JP 2017016440 W JP2017016440 W JP 2017016440W WO 2017188283 A1 WO2017188283 A1 WO 2017188283A1
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resin foam
nonwoven fabric
adhesive
resin
layer
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PCT/JP2017/016440
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French (fr)
Japanese (ja)
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政美 小宮山
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旭化成建材株式会社
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance

Abstract

The present invention provides: a resin foam in which the strength of adhesion between a nonwoven fabric and a resin foam layer is further improved so as to prevent the nonwoven fabric from peeling off even when being handled roughly to some extent and the appearance of which is easily maintained; and a composite which is obtained by joining the resin foam and an external member together, which is less likely to be disassembled than conventional composites, and which has excellent handleability. The resin foam according to the present invention is formed by layering a resin foam layer directly on a nonwoven fabric of which the elongation percentage is 45-250% both in the lengthwise and crosswise directions and of which the tensile strength is at least 100 N/5 cm width in the lengthwise direction and at least 50 N/5 cm width in the crosswise direction but is not higher than 600 N/5 cm width in the lengthwise and crosswise directions.

Description

Resin foam and complexes

The present invention is a resin foam and a resin foam layer and the nonwoven fabric are laminated, and the said resin foam and the outer member, and bonded via a bonding layer formed on the nonwoven fabric laminated on the foamed resin layer complex composed of about.

Resin foam and resin foam layer and the nonwoven fabric are laminated, in addition to use it alone, there is a case to be used in a variety of applications by bonding the outer member. The resin foam and complex is bonded to the outer member, for example, sandwich panels with metal panels as an external member, such as a waterproof heat-insulating construction using a resin sheet is known.

However, the location for the adhesion strength between resin foam layer and the nonwoven fabric in the resin foam is low, the complex is bonded to the said resin foam and the outer member, required time, or it to use this after installation, the nonwoven fabric is peeled off from the resin foam layer, integral with the resin foam and the outer member had anxiety lost.

In contrast, in Patent Document 1, the surface of the resin foam, or less fiber diameter 18 microns, and basis weight by using a synthetic fiber nonwoven fabric is 15 g / m 2 or more, adhesion between the resin foam layer and the nonwoven fabric We are trying to improve strength.

JP 11-198332 discloses

However, in the method described in Patent Document 1, the adhesive strength between the resin foam layer and the surface the nonwoven fabric is only about 200 g / 3 cm wide. The present invention, the adhesive strength between the nonwoven fabric and the foamed resin layer further improves, not less rough dealing even nonwoven peeling, together with the maintenance of aesthetics provide easy resin foam was bonded to the outer member in the complex, difficult to peel than ever, it is an object to provide a composite with excellent handling properties.

The present invention, in order to achieve the above object, a nonwoven fabric is laminated on the foamed resin layer, it found that is possible to use a nonwoven fabric having a specific elongation and tensile strength is effective, have accomplished the present invention .
That is, the present invention provides the following [1] to [4].
[1] JIS L 1913: measured by standard time test method stipulated in 2010 elongation, none of the longitudinal and transverse direction of 45% or more and 250% or less, and, JIS L 1913: 2010 tensile strength measured in the test method standard time defined is in the longitudinal direction 100 N / 5 cm width or more, with at 50 N / 5 cm width or more in the transverse direction, both the longitudinal and transverse directions 600N / 5 cm width or less and the nonwoven fabric is, and a resin foam layer, formed by laminating directly, resin foam.
[2]
The foamed resin layer adhesive coexist within the adjacent non-woven fabric, and the presence of the adhesive on the interface between the nonwoven fabric and the foamed resin layer is 50% or less, the resin according to [1] foam.
[3] the resin foam and the outer member, formed by joining through a bonding layer formed on the nonwoven fabric composite.
[4] The bonding layer is a layer composed of adhesive, said co-exist with a portion with a portion of the adhesive nonwoven fabric, the presence of the adhesive on the interface between the nonwoven fabric and the foamed resin layer There is 50% or less, the complex according to [3].

As described above, the resin foams of the present invention, the surface of the nonwoven fabric is hardly peeled off because they strongly adhered to the resin foam layer, over without impairment of appearance of the resin foam be handled somewhat rough, strong in bonding with the outer member, it can provide an excellent complex handling.

Figure 1 is a schematic diagram showing an example of a resin foam of the present embodiment (sectional view). Figure 2 is a schematic diagram showing an example of the composite body of the present embodiment (sectional view). Figure 3 is a schematic diagram showing an example of the composite body of the present embodiment (sectional view).

Hereinafter, embodiments of the present invention (hereinafter, sometimes referred to as "the present embodiment".) Will be described in detail.

Resin foam of the present invention, JIS L 1913: measured by standard time test method stipulated in 2010 elongation, none of the longitudinal and transverse direction of 45% or more and 250% or less, and, JIS L 1913: tensile strength measured in the standard time of the test method specified in 2010, in the longitudinal direction 100 N / 5 cm width or more, with at 50 N / 5 cm width or more in the transverse direction, both the longitudinal and transverse directions and the nonwoven fabric is 600N / 5 cm width or less, and a resin foam layer formed by laminating directly. In this specification, refers to the direction of production of the nonwoven fabric to the longitudinal direction refers to a direction perpendicular to the longitudinal direction of the nonwoven fabric surface and transverse direction.
In the resin foam of the present invention, the inside of the nonwoven adjacent to the foamed resin layer, but the adhesive may coexist, the adhesive on the interface between the nonwoven fabric and the foamed resin layer is the proportion of the portion present is 50% or less.
Figure 1 is a schematic sectional view showing an example of the resin foam of the present embodiment. Resin foam 1 of the present embodiment, the nonwoven fabric 2 and the resin foam layer 3 is laminated directly.

As the resin foam layer in the resin foam of the present embodiment, various foamed resins are available. The resin used in the resin foam layer, for example, polyethylene, polystyrene, polyurethane, polyisocyanurate, but like phenol resin, polyurethane or polyisocyanurate cured by heating at moderate temperatures, phenolic resin , preferable in that it does not restrict the melting point of the nonwoven fabric to be used.
Note that when using these resin foam layer insulation purposes, it is preferable density of 15 kg / m 3 or more 60 kg / m 3 or less. More preferably not more than 20 kg / m 3 or more 50 kg / m 3. Also, the closed cell ratio is preferably at least 80%, more preferably in the range of 85% or more, furthermore preferably 90% or more.
Here, the density refers to a value measured by the method described in the following item of (Evaluation method) "(1) Density of resin foam layer." Also, the closed cell ratio is a value measured by the method described in "(2) closed cell content of the resin foam layer" below (Evaluation method).

As the foaming agent used in forming the resin foam layer, it is conceivable to use a hydrocarbon. The hydrocarbon, cyclic or linear alkane of 3-7 carbon atoms, alkenes, alkynes are preferred, specifically, butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and cyclohexane. Among them, normal pentane, isopentane, cyclopentane, pentane such as neopentane, and n-butane, isobutane, butanes cyclobutane or the like is preferably used. It These hydrocarbons may be used singly or may be used in combination of two or more.

When a mixture of hydrocarbons and other components as a foaming agent, the content of hydrocarbons in the blowing agent is preferably 10 mass% or more, more preferably at least 20 wt%, 30 wt it is more preferably not less than%.

Further, as a foaming agent, chlorinated hydro fluoroolefin, may be used in the constituent hydro fluoroolefin blowing agent such as a non-chlorinated hydro fluoroolefin. As the chlorinated hydro fluoroolefin, specifically, 1-chloro-3,3,3-trifluoropropene (product name: Solstice (TM) LBA) and the like, non-chlorinated hydro fluoroolefin as is specifically 1,3,3,3-tetrafluoro-1-propene (product name: Solstice (TM) 1234ze), 2,3,3,3-tetrafluoro-1-propene, 1 , and the like 1,1,4,4,4- hexafluoro-2-butene. Chlorinated hydro fluoroolefin and / or non-chlorinated hydro fluoroolefin may be used alone or may be used in combination of two or more. With hydro fluoroolefin blowing agent, it is also possible to further increase the adhesive strength between the nonwoven fabric.

Blowing agents described above can be used in combination both, respectively. The amount of blowing agent may be about 2 to 15% by weight relative to the resin contained in the foamable resin composition used for forming a resin foam layer.

When the resin foam may comprise a foam nucleating agent. The foam nucleating agent, e.g., nitrogen, helium, argon, boiling point include lower than 50 ° C. Low boiling point material than said blowing agent such as air. Further, the foam nucleating agent is, for example, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, Bald earth (kaolin), silica flour, silica sand, mica, calcium silicate powder, wollastonite, glass powder , glass beads, fly ash, silica fume, gypsum powder, borax, slag powder, aluminous cement, inorganic powders such as Portland cement, may be an organic powder such as solid foam nucleating agent such as resin foam powder. The foam nucleating agent may be used alone or may be used in combination of two or more.

Amount with respect to the foaming agent of the foam nucleating agent, the relative blowing agent total amount (100 mass%) is preferably from 0.1 mass% to 1.0 mass%, 0.2 mass% 0.6 mass% or less is more preferable. If the addition amount of the foam nucleating agent is more than 0.1 mass% uniform foaming is likely to occur, The amount of foam nucleating agent is not more than 1.0 mass%, foaming of the resin is not excessively promoted Therefore, easier to penetrate the foamed resin to the nonwoven fabric, the adhesion strength is easily secured.
Yet another of the foam nucleating agent, curing agents, surfactants, plasticizers, may also be included bulking agent.

Nonwoven fabric used for the resin foam of the present embodiment, JIS L 1913: elongation measured at a defined standard time test method 2010, vertical and horizontal both 45% or more, 250% or less . If 45% or more, to improve adhesive strength between the resin foam layer is not more than 250%, when is bonded to the external member hardly deformation force due to the nonwoven fabric itself received from the outside is happening. More preferably the longitudinal direction 200% 60% or less, the horizontal direction is 200% or less than 60%. More preferably the longitudinal direction 200% 70% or less, the horizontal direction is 200% or less than 70%.
Incidentally, the elongation of the nonwoven fabric refers to a value measured by the method described in "(3) elongation of the nonwoven fabric" in below (Evaluation method).

The non-woven fabric, JIS L 1913: tensile strength measured at a defined standard time test method 2010, in the longitudinal direction 100 N / 5 cm width or more, in the transverse direction together is 50 N / 5 cm width or more, the longitudinal and transverse directions There are both 600N / 5cm width below. And longitudinal direction 100 N / 5 cm width or more, if the lateral 50/5 cm width or more, in producing a resin foam of the present embodiment, together with possible to avoid the risk of non-woven fabric is torn in the production process It may maintain the elongation rate as long 600N / 5 cm width or less. More preferably the longitudinal direction 150 N / 5 cm width or more, 500 N / 5 cm width or less, the transverse direction is less 70N / 5 cm width or more 500 N / 5 cm width.
The tensile strength of the nonwoven fabric refers to a value measured by the method described in "(4) Tensile strength of nonwoven fabric" of the later (Evaluation method).

Also, the basis weight of the nonwoven fabric is preferably in a 50 g / m 2 or more. When forming the complex as long as 50 g / m 2 or more, in the case of using a liquid adhesive type as an adhesive to be described later, coexisting portion to be described later is hard to reach the resin foam layer. More preferably 80 g / m 2 or more, still more preferably 100 g / m 2 or more. Further, it is preferable from the viewpoint of build appropriately resin foam layer is 300 g / m 2 or less.
Incidentally, the basis weight of the nonwoven fabric refers to a value measured by the method described in "(5) weight per unit area of ​​the nonwoven fabric" in below (Evaluation method).

Further, the thickness of the nonwoven fabric is preferably at least 0.3 mm, more preferably 0.6mm or more. Further, it is preferable that the 5mm or less. If 0.3mm or more, when forming the complex, in the case of using a liquid adhesive type bonding layer to be described later, becomes difficult coexisting portion to be described later reaches the resin foam layer, if 5mm or less easily make high thermal insulation performance resin foam layer.
Incidentally, the nonwoven thickness is a value measured by the method described in "(6) Thickness of the nonwoven fabric" in below (Evaluation method).

As the nonwoven fabric, as in the non-woven fabric manufactured by a nonwoven fabric, a needle punch method, water jet method or the like produced by a dry method or a spun-bonding method or the like, adhesive bonding or heat sealing (fusion), hooks in such a way that the entangling by per needle and water pressure, nonwoven fabric or the like made through the intentional step of fixing between fibers in order to maintain the strength of the fabric and the like.
The types of fibers used in the nonwoven fabric used in the present embodiment, it is possible to use various fibers satisfying the tensile strength of the aforementioned the aforementioned elongation, the ease of availability polyester, such as polypropylene the synthetic resin preferably fibers as a raw material, particularly polypropylene are preferred.

In the resin foam of the present embodiment, the adhesive inside the nonwoven fabric may coexist. Here, the adhesive inside the nonwoven fabric coexist, for example, a result of the resin foam of the present embodiment has a liquid adhesive is applied in advance nonwoven to bond the outer member, elaborate bleeding adhesive inside the nonwoven fabric If, and the like.

However, in this case, it is preferable that the ratio of the portion where there is adhesive on the interface between the nonwoven fabric and resin foam layer is not more than 50%. Exceeds 50%, the peeling strength between the nonwoven fabric and the foamed resin layer is lowered. A more preferred range of the ratio of the portion there is adhesive on the interface between the nonwoven fabric and the foamed resin layer is 30% or less, more preferably 5% or less.
The ratio of the portion there is adhesive on the interface between the nonwoven fabric and the foamed resin layer, the "(8) The proportion of the adhesive in the interface between the nonwoven fabric and resin foam layer" below (Evaluation Method) It refers to a value measured by the method described.

Complexes of the present invention, the resin foam and the outer member is formed by joining through a bonding layer formed on the nonwoven fabric.
Figure 2 is a diagram showing an example of the composite body of the present embodiment. Complex 4 of the present embodiment, resin foam and the nonwoven fabric 2 and the resin foam layer 3 is formed by laminating directly, via a bonding layer 5 formed on the nonwoven fabric 2, is bonded to the outer member 7 .
Figure 3 also illustrates an example of a complex of the present embodiment similarly to Fig. In complex 4, the bonding layer 5 is a layer made of an adhesive, the nonwoven fabric 2, a portion of the adhesive to penetrate the part, coexist portion 6 where the nonwoven fabric and the adhesive coexist Existing.

Here, the bonding layer, wherein an external member and a layer for bonding the nonwoven fabric, for example, a layer consisting of double-sided pressure-sensitive adhesive sheet, and an adhesive layer or the like.
Incidentally, using a liquid adhesive to the bonding layer, the coexistence of adhesive inside the nonwoven fabric, when the ratio of the portion that there is adhesive on the interface between the nonwoven fabric and the foamed resin layer is less than 50%, the nonwoven fabric for increasing peel strength between the outer member and the resin foam or the peel strength between the resin foam layer, the use of liquid adhesive as a bonding layer, more preferably.

The adhesive used to form the bonding layer, based on the material of the nonwoven fabric both said outer member, of the type capable of bonding these is used. Above all the liquid adhesive coexist adhesive therein nonwoven using, when the ratio of the portion there is adhesive on the interface between the nonwoven fabric and the foamed resin layer is 50% or less, the peeling strength between the nonwoven fabric and the foamed resin layer since the peel strength between the outer member and the foamed resin layer is increased to higher, more preferably used. Specific examples of the liquid adhesive, SBR adhesive, nitrile rubber adhesive, epoxy adhesive, and the like.

When using a liquid adhesive, it is preferable that the viscosity is 3000 mPa · s or more. If the viscosity is 3000 mPa · s or more, the liquid adhesive tends prevents would reach the foamed resin layer through the thickness direction of the nonwoven fabric. More preferably 3500 mPa · s or more, and still more preferably 4500 mPa · s or more.

As the said outer member, a resin sheet, resin plate, a metal plate, it is possible to use a wooden board or the like.

(Evaluation method)
Listed measuring method of the above-mentioned physical properties as follows.
(1) cut out a rectangular parallelepiped 20cm square in any thickness from density resin foam layer of the foamed resin layer as a sample, determined by measuring the mass and volume of the sample. Measured according to JIS K 7222.

(2) in the center in the thickness direction of the closed cell ratio resin foam layer of the foamed resin layer, with a band saw, if the thickness of the resin foam layer is not less than 25mm cut a cube of 25mm square as a sample, the thickness of the resin foam layer If is less than 25mm having a thickness of the rear surface member removed, by cutting a rectangular parallelepiped 25mm as a sample vertically and horizontally, the air comparison type densimeter (1000 type, Tokyo Science Co., Ltd.) by standard use of a sample volume V (cm 3) to measure. Closed cell content in the foamed resin layer, as the following equation, the sample volume V and the sample mass W (g) and the value obtained by subtracting the volume of the calculated cell walls and a density ρ of the resin composition constituting the resin foam layer and a value defined by the volume Va apparent calculated from the outer dimensions (cm 3) of the sample are measured in accordance with ASTM D 2856 (C method).
Closed cell ratio (%) = ((V-W / ρ) / Va) × 100

(3) elongation of the nonwoven fabric used as a member of the elongation resin foam nonwoven nonwoven alone as it JIS L 1913: measured at standard time test method stipulated in 2010.
When the nonwoven fabric forms a part of the resin foam, a nonwoven fabric having a resin foam layer, as possible cut from the resin foam as part of the only resin foam layer is reduced, a resin foam layer entangled nonwoven fabric the break by physical method, after being frozen by immersion in liquid nitrogen, breaking by physical methods, immersing only the resin foam layer in solvent solubility decomposes, etc., suitable in accordance with the nature of the resin foam layer by selecting the method to remove the resin foam layer. If there is coexistence portion between the nonwoven fabric inside adhesives, breaking by physical methods adhesive coexisting, breaking by physical methods after frozen by immersion in liquid nitrogen, and dissolved only adhesive like immersed in a solvent decomposing, removing the adhesive by choosing the appropriate method depending on the nature of the adhesive. Thereafter, the resulting nonwoven fabric produced from the resin foam JIS L 1913: perform measurements at Time test method stipulated in 2010.
Nonwoven forms a complex, if present coexistence portion between the nonwoven fabric and the bonding layer, a nonwoven fabric having a bonding layer and the resin foam layer, as possible points of only resin foam layer is reduced, and , so that fewer locations only possible bonding layer, cut from the complex, after which the resin foam layer and adhesive entangled nonwoven fabric break by physical methods, by physical methods after frozen by immersion in liquid nitrogen breaking, or the like immersed resin foam layer and / or adhesive only on solvent solubility decomposes, a resin foam layer and the bonding layer is removed by selecting the appropriate method depending on the nature of the resin foam layer and the bonding layer, Thereafter, the nonwoven fabric obtained from composite JIS L 1913: perform measurements at Time test method stipulated in 2010.

(4) Tensile strength of nonwoven fabric is used as a member of the tensile strength resin foam nonwoven nonwoven alone as it JIS L 1913: at Time test method stipulated in 2010, measured. If the nonwoven fabric forms a part of the resin foam or complexes in the same manner as in the above (3) after removal of the non-woven fabric, JIS L 1913: measured at standard time test method stipulated in 2010.

(5) weight per unit area of ​​the nonwoven fabric used as a member of the basis weight resin foam nonwoven nonwoven alone as it JIS L 1913: at Time test method stipulated in 2010, measured. Further, after if nonwoven forms part of the resin foam and complexes obtained by extracting only nonwoven fabric in the same manner as in the above (3), JIS L 1913: at Time test method stipulated in 2010 Measure.

(6) Thickness of the nonwoven fabric used as a member having a thickness of the resin foam nonwoven nonwoven simple as JIS L 1913: measured at standard time test method stipulated in 2010. If the nonwoven fabric forms a part of the resin foam or complexes in the same manner as in the above (3) after removing only the non-woven fabric, JIS L 1913: measured at standard time test method stipulated in 2010 .

(7) the adhesive strength produced resin foam of nonwoven fabric and a resin foam layer, an area of ​​width 25 mm, length 150 mm, cut out resin foam rod-shaped, an evaluation sample. , Fix the evaluation samples, picked up the nonwoven fabric from the longitudinal ends, it performs a 90 ° peel strength test of the nonwoven fabric by Shimadzu Autograph AG-X. Tensile rate of non-woven fabric is a 200mm / min. In the case of cutting out an evaluation sample of a resin foam is continuously molded, the length direction of the evaluation sample to the flow direction of the continuous production.

(8) non-woven fabric and the resin foam layer of the presence proportion adhesive of the adhesive on the surface to cut anywhere in the resin foam containing within nonwoven with a razor blade to expose the cross section in the thickness direction, 100 times the cross section was observed by SEM at a magnification occupies the interface entire length of the nonwoven fabric and the foamed resin layer in the observation range, the adhesive calculates the ratio of the length of a portion has reached the interface. Similar measurement was carried out at any of all five, and the average value and the existence ratio of the adhesive on the interface between the nonwoven fabric and resin foam layer.

(9) and adhesive strength outer member of the outer member and the resin foam, width 25 mm, in the area of ​​length 150 mm, a resin foam bonded, to measure the strength required upon the release of the outer member. External member in the case of the resin sheet, and picked up the resin sheet of the evaluation sample ends in the same manner as in (7), measures the bond strength. The resin molded body and the metal plate outer member is thick, wood or the like, when the flexible having no material, fix a resin foam in a suitable way, immediately the end of the outer member to the member sandwiched between the jig performs a 90 ° peel strength test by Shimadzu Autograph AG-X. The speed of pulling and 200mm / min.

Hereinafter, the present invention will be described in more detail with reference to Examples.
(Example 1)
Prepared phenolic resin foam in the following manner, was evaluated further to produce a complex with the vinyl chloride sheet.
<Synthesis of phenol resin>
Reactor was charged with 52 wt% aqueous formaldehyde solution 3500kg and 99 wt% phenol 2510Kg, stirred with a propeller-type stirrer to prepare a reactor internal liquid temperature at 40 ° C. by temperature controller. Then heated while applying a 50 wt% aqueous sodium hydroxide solution, the reaction was allowed to proceed. At the stage where the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction was cooled, urea (equivalent to 15 mol% of formaldehyde charged amount) 570 kg was added. Thereafter, the reaction solution was cooled to 30 ° C., and neutralized to pH 6.4 with 50 wt% aqueous solution of p-toluenesulfonic acid monohydrate. 60 ° C. In to dehydration treatment, where the viscosity and water content of the obtained reaction mixture (thermosetting resin composition) was measured, the viscosity at 40 ° C. is 5,800mPa · s, water content is 5 wt% met It was.
<Preparation of phenolic resin composition>
Phenol resin with respect to the reaction solution 96.5 parts by mass of the dewatered mainly ethylene oxide as a surface active agent - block copolymer of propylene oxide (BASF, product name "Pluronic (TM) F-127 ") were mixed at a ratio of 3.5 parts by weight.
The obtained surfactant-containing phenolic resin composition 100 parts by weight of mixture 7 parts by weight of isopentane 50% by weight isobutane 50 wt% as a foaming agent, 80 wt% xylene sulfonic acid and diethylene glycol 20 wt as a curing catalyst the mixture 11 parts by weight of a%, is supplied to a mixing head controlled at 25 ° C., to obtain a phenol resin composition.
Here, the mixing machine used, there is an upper surfactant containing phenolic resin composition on the side surface, and inlet of the blowing agent comprises a inlet of the curing catalyst on the side surface near the center of the agitating portion that rotor is stirred , since the stirring unit was used pin mixer which is connected to the distribution unit having a nozzle for discharging the foam. A plurality of nozzles are designed to mixed phenolic resin composition is uniformly distributed. Further, as the center side and bottom of the mixer can be measured temperature in the system, the temperature sensor is set. Further comprises a jacket temperature control for enabling the mixer temperature adjustment. Temperature measured at the temperature sensor was 36.4 ° C..
<Production of phenolic foam>
As the upper and lower non-woven fabric, JIS L 1913: based on the 2010, basis weight 200 g / m 2, it was measured to thickness 0.76 mm, made of polypropylene fiber having a circular cross section with a diameter 25 [mu] m, vertical elongation 70% , lateral elongation of 90% longitudinal tensile strength 310N / 5 cm width, the phenolic resin through a multiport distribution pipe lateral tensile strength thereon while moving the spunbonded nonwoven fabric of 200 N / 5 cm width the composition was supplied. Phenolic resin composition supplied onto the nonwoven fabric, sandwiched further nonwoven vertically coated with the same kind of non-woven thereon, the feed to the slat-type double conveyor 85 ° C., after curing at 15 minute residence time to obtain a resin foam having a thickness of 30mm and 2 hours curing at 110 ° C. oven. Slat-type double conveyor was utilized in this case, loophole of water was provided to the moisture generated during curing can be discharged to the outside. Density of foamed resin layer of the molded phenolic foam is 27 kg / m 3 density of the phenolic resin composition as 1.3 kg / cm 3, the closed cell ratio was 90%.
This way, the resin foam was produced to measure the bond strength between the nonwoven fabric and the foamed resin layer according to the method of (7).
Subsequently, on the surface nonwoven Similarly produced resin foam, including methyl ethyl ketone 55 mass%, a nitrile rubber-based liquid adhesive having a viscosity of 4500 mPa · s, 1 m 2 per then 200g coated, vinyl chloride having a thickness of 2mm by applying a liquid adhesive in the same manner on one side of the sheet, and a complex after 15 minutes by bonding the adhesive coated surface of the adhesive coated surface and the resin foam vinyl chloride sheet. Then, the existence ratio of the adhesive on the interface between the nonwoven fabric and the foamed resin layer according to the method of (8) to evaluate the adhesive strength of vinyl chloride sheet and a resin foam by the method of (9).
Incidentally, the resin foam, the resin foam layer with nonwoven fabric cut, the resin foam layer obtained by removing by breaking physical methods so as not to affect the fibers constituting the nonwoven fabric according to means described in the above (3) measurement of the elongation and tensile strength of the nonwoven fabric, the elongation longitudinal 72% transverse 88%, tensile strength machine direction is 311N / 5 cm width, lateral was 197N / 5cm width.
Furthermore, from the complex, the cut resin foam layer with nonwoven according unit described in (3), resin foam layer removal by breaking physical methods so as not to affect the fibers constituting the nonwoven fabric, the adhesive layer measurement of the elongation and tensile strength of the nonwoven fabric obtained by removing dissolved in acetone, the elongation longitudinal 74%, a transverse direction is 91%, the tensile strength is longitudinally 312N / 5 cm width, lateral is 200 N / 5 cm width, elongation, none of the tensile strength was almost the same as the nonwoven fabric used as members of the resin foam and composites.
Further, the basis weight of the nonwoven fabric obtained from the resin foam 199 g / m 2, the thickness is 0.75mm, basis weight of the nonwoven fabric obtained from composite 197 g / m 2, the thickness is at 0.75mm , basis weight was approximately equal to none of thickness was used as a member of the resin foam and the composite nonwoven fabric.

(Example 2)
As the upper and lower non-woven fabric, JIS L 1913: based on the 2010, basis weight 200 g / m 2, it was measured to thickness 1.65 mm, made of polypropylene fiber having a circular cross section with a diameter 25 [mu] m, vertical elongation 181% , lateral elongation 191% longitudinal tensile strength 242n / 5 cm width, the lateral tensile strength of 167N / 5cm width of the spunbond needle punched composite molded nonwoven, except for using the example 1 and in the same manner by molding a resin foam, the adhesive strength was measured between the nonwoven fabric and the foamed resin layer according to the method of (7).
Further, on the surface nonwoven Similarly produced resin foam, including methyl ethyl ketone 40 mass%, the SBR-based liquid adhesive having a viscosity of 3000 mPa · s, 1 m 2 per then 200g coating thickness thereon after a lapse of 15 minutes It was complexed paste 2mm vinyl chloride sheet of the. Thereafter, in the same manner as in Example 1 to evaluate the adhesion strength between the existing ratio, PVC sheeting and resin foam adhesive on the interface between the nonwoven fabric and resin foam layer.
In the same manner as in Example 1, a nonwoven fabric obtained from obtained nonwoven and complexes derived from resin foam, elongation, tensile strength, basis weight was measured for thickness, the resin foam and complexes It was almost equal to the non-woven fabric used as members.

(Example 3)
As the upper and lower non-woven fabric, JIS L 1913: based on the 2010, basis weight 100 g / m 2, was measured to the thickness 1.0 mm, made of crimped polypropylene fiber cross-section has a width 40 [mu] m, the flat shape having a thickness of 5 [mu] m, vertical direction elongation of 90%, 140% transverse elongation, except that the longitudinal direction of the tensile strength 245 N / 5 cm width, in the transverse direction tensile strength using spunbonded nonwoven 80 N / 5 cm width, example 1 and in the same manner by molding a resin foam, the adhesive strength was measured between the nonwoven fabric and the foamed resin layer according to the method of (7).
Further, on the surface nonwoven Similarly produced resin foam, including methyl ethyl ketone 60 mass%, a nitrile rubber-based liquid adhesive having a viscosity of 3500 mPa · s, 1 m 2 per then 200g coated, vinyl chloride having a thickness of 2mm sheet also applying the liquid adhesive in the same manner on one side of, and a complex after 15 minutes by bonding the adhesive coated surface of the adhesive coated surface and the resin foam vinyl chloride sheet. Thereafter, in the same manner as in Example 1 to evaluate the adhesion strength between the existing ratio, a vinyl chloride sheet and a resin foam adhesive on the interface between the nonwoven fabric and resin foam layer.
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from obtained nonwoven and complexes derived from resin foam, elongation, tensile strength, basis weight was measured for thickness, the resin foam and complexes It was almost equal to the non-woven fabric used as members.

(Example 4)
As the upper and lower non-woven fabric, JIS L 1913: based on the 2010, basis weight 80 g / m 2, was measured to thickness 0.73 mm, made of crimped polypropylene fiber cross-section has a width 40 [mu] m, the flat shape having a thickness of 5 [mu] m, vertical direction elongation of 78%, 102% transverse elongation, except that the longitudinal direction of the tensile strength 176N / 5 cm width, in the transverse direction tensile strength using spunbonded nonwoven fabric 57N / 5 cm width, example 1 and in the same manner by molding a resin foam, the adhesive strength between the resin foam surface nonwoven fabric and a resin foam layer was measured by the method (7).
Was also produced in the same manner, on the surface the nonwoven fabric of the resin foam, including methyl ethyl ketone 40 mass%, the SBR-based liquid adhesive having a viscosity of 3000 mPa · s, 1 m 2 per then 200g coating thickness 2mm to 15 minutes after It was complexed by bonding the vinyl chloride sheet. Thereafter, in the same manner as in Example 1 to evaluate the adhesion strength between the existing ratio, a vinyl chloride sheet and a resin foam adhesive on the interface between the nonwoven fabric and resin foam layer.
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from obtained nonwoven and complexes derived from resin foam, elongation, tensile strength, basis weight was measured for thickness, the resin foam and complexes It was almost equal to the non-woven fabric used as members.

(Comparative Example 1)
JIS L 1913: based on the 2010, basis weight 100 g / m 2, it was measured to thickness 0.48 mm, made of polypropylene fiber having a circular cross-section of 20μ diameter, longitudinal elongation of 30% in the transverse direction elongation 40%, machine direction tensile strength of 350 N / 5 cm width, except that the transverse direction of the tensile strength using the spunbonded nonwoven fabric of 150 N / 5 cm width, in the same manner as in example 1 by molding a resin foam , the adhesive strength was measured between the nonwoven fabric and the foamed resin layer according to the method of (7). Since the adhesive strength was small, it was discontinued the production of the complex.
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from the resin foam, elongation, tensile strength, basis weight was measured thickness was approximately equal to the nonwoven fabric used as members of the resin foam .

(Comparative Example 2)
JIS L 1913: based on the 2010, basis weight 130 g / m 2, it was measured to thickness 0.61 mm, made of nylon fiber having a circular cross-section of 20μ diameter, longitudinal elongation of 40% in the transverse direction elongation 55%, machine direction tensile strength of 550 N / 5 cm width, except that the transverse direction of the tensile strength using the spunbonded nonwoven fabric of 210N / 5 cm width, in the same manner as in example 1 by molding a resin foam , the adhesive strength was measured between the nonwoven fabric and the foamed resin layer according to the method of (7). Since the adhesive strength was small, it was discontinued the production of the complex.
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from the resin foam, elongation, tensile strength, basis weight was measured thickness was approximately equal to the nonwoven fabric used as members of the resin foam .

(Comparative Example 3)
JIS L 1913: based on the 2010, basis weight 30 g / m 2, was measured to thickness 0.25 mm, made of polypropylene fiber having a circular cross-section of 20μ diameter, longitudinal elongation of 50% in the transverse direction 70% elongation, longitudinal tensile strength 85N / 5 cm width, except that the transverse direction of the tensile strength using the spunbonded nonwoven fabric of 22N / 5 cm width, in the same manner as in example 1 by molding a resin foam , the adhesive strength was measured between the nonwoven fabric and the foamed resin layer according to the method of (7). Since the adhesive strength was small, it was discontinued the production of the complex.
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from the resin foam, elongation, tensile strength, basis weight was measured thickness was approximately equal to the nonwoven fabric used as members of the resin foam .

(Reference Example)
For resin foam produced in Example 1, on the surface the nonwoven fabric of the resin foam, including methyl ethyl ketone 50 mass%, the SBR-based liquid adhesive having a viscosity of 2000 mPa · s, 1 m 2 per then 200g coating, after 15 minutes was a complex later paste the PVC sheet from above. Then, to evaluate the adhesion strength of the existing ratio of the adhesive, a vinyl chloride sheet and a resin foam by the method of (9) on the interface between the nonwoven fabric and the foamed resin layer by the method of (8).
Incidentally, in the same manner as in Example 1, a nonwoven fabric obtained from obtained nonwoven and complexes derived from resin foam, elongation, tensile strength, basis weight was measured for thickness, the resin foam and complexes It was almost equal to the non-woven fabric used as members.

Figure JPOXMLDOC01-appb-T000001

Resin foam of the present embodiment, since high adhesive strength between the nonwoven fabric and the foamed resin layer, not less rough dealing even nonwoven peeling, is joined to the outer member with an easy to maintain aesthetic appearance of the resin foam hardly degradation than conventional when no complex with Te, can be a complex having an excellent handling property. Resin foam of the present embodiment, and the complex of the present embodiment, for example, can be used as a product available in places that require thermal insulation.

1 resin foam 2 nonwoven fabric 3 resin foam layer 4 complex 5 bonding layer 6 nonwoven and the adhesive coexist coexisting portion 7 outside member

Claims (4)

  1. JIS L 1913: measured elongation at Time test method stipulated in 2010, both the longitudinal and transverse direction of 45% or more and 250% or less, and, JIS L 1913: stipulated in 2010 tensile strength measured by test method standard time was found in the longitudinal direction 100 N / 5 cm width or more, with at 50 N / 5 cm width or more in the transverse direction, both the longitudinal and transverse direction is 600N / 5 cm width or less nonwoven When, and a resin foam layer, formed by laminating directly, resin foam.
  2. The resin adjacent to the foam layer adhesive coexist inside the nonwoven fabric, and the presence of the adhesive on the interface between the nonwoven fabric and the foamed resin layer is 50% or less, according to claim 1 resin foam.
  3. Claim 1 or the resin foam and the outer member according to 2, complexes formed by joining through a bonding layer formed on the nonwoven fabric.
  4. The bonding layer is a layer made of an adhesive,
    It said portion and a portion coexist in the adhesive nonwoven fabric, the presence of the adhesive on the interface between the nonwoven fabric and the foamed resin layer is 50% or less, composite according to claim 3.
PCT/JP2017/016440 2016-04-28 2017-04-25 Resin foam and composite WO2017188283A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11198332A (en) * 1998-01-07 1999-07-27 Asahi Chem Ind Co Ltd Phenolic resin foam laminated sheet, manufacture thereof and executing method thereof
US6855424B1 (en) * 1998-12-28 2005-02-15 Kinberly-Clark Worldwide, Inc. Breathable composite elastic material having a cellular elastomeric film layer and method of making same
JP2005047158A (en) * 2003-07-29 2005-02-24 Asahi Kasei Construction Materials Co Ltd Heat insulating board
JP2006110829A (en) * 2004-10-14 2006-04-27 Nitto Boseki Co Ltd Phenol resin foam laminated sheet and its manufacturing method
JP2009090554A (en) * 2007-10-09 2009-04-30 Asahi Kasei Construction Materials Co Ltd Flame-retardant phenol resin foam laminated sheet and its manufacturing method
WO2015034069A1 (en) * 2013-09-06 2015-03-12 三井化学株式会社 Nonwoven fabric laminate for foaming molding, method for producing nonwoven fabric laminate for foaming molding, urethane foaming molding composite using nonwoven fabric laminate, vehicle seat, and chair

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11198332A (en) * 1998-01-07 1999-07-27 Asahi Chem Ind Co Ltd Phenolic resin foam laminated sheet, manufacture thereof and executing method thereof
US6855424B1 (en) * 1998-12-28 2005-02-15 Kinberly-Clark Worldwide, Inc. Breathable composite elastic material having a cellular elastomeric film layer and method of making same
JP2005047158A (en) * 2003-07-29 2005-02-24 Asahi Kasei Construction Materials Co Ltd Heat insulating board
JP2006110829A (en) * 2004-10-14 2006-04-27 Nitto Boseki Co Ltd Phenol resin foam laminated sheet and its manufacturing method
JP2009090554A (en) * 2007-10-09 2009-04-30 Asahi Kasei Construction Materials Co Ltd Flame-retardant phenol resin foam laminated sheet and its manufacturing method
WO2015034069A1 (en) * 2013-09-06 2015-03-12 三井化学株式会社 Nonwoven fabric laminate for foaming molding, method for producing nonwoven fabric laminate for foaming molding, urethane foaming molding composite using nonwoven fabric laminate, vehicle seat, and chair

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