JP2021001534A - Face material - Google Patents

Abstract

To provide face material constituting interior material or exterior material.SOLUTION: The inventors found that the problem in which irregularities not intended are present on a main surface derived from an acrylic resin layer occurring in interior material or exterior material prepared by heating and forming face material that 'has a print containing particles on at least one main surface of a fiber assembly and has the acrylic resin layer on the print as well' or the problem in which the particle contained in the print falls from the main surface side derived from the acrylic resin layer can be restricted by using the face material which satisfies the article (i) evaluated in the measurement according to the invention.SELECTED DRAWING: Figure 1

Description

The present invention relates to a surface material that can form an interior material or an exterior material.

For example, as disclosed in Japanese Patent Application Laid-Open No. 2015-104948 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2016-147466 (Patent Document 2), as constituent members of surface materials that can form interior materials and exterior materials of automobiles, Traditionally, fiber aggregates (eg, fiber webs, non-woven fabrics, woven fabrics, knitted fabrics, etc.) have been used. In addition, Patent Document 1 and Patent Document 2 disclose a surface material in which a print containing particles is provided on one main surface of a fiber aggregate, and further, an acrylic resin or the like is provided on the print. It is disclosed that a resin layer (protective layer) may be provided.

JP 2015-104848 JP 2016-147466

The applicant of the present application has a surface material having a print containing particles on at least one main surface of the fiber aggregate and an acrylic resin layer on the print, referring to the above-mentioned prior art. Was examined.
However, when a surface material satisfying such a configuration is sandwiched between molds and heat-molded to prepare an interior material or an exterior material, the prepared interior material or exterior material is found.
・ The problem that there are unintended irregularities on the main surface derived from the acrylic resin layer,
There has occurred. In addition
-The problem that particles contained in the print may fall off from the main surface side derived from the acrylic resin layer.
Occasionally occurred.

The present invention is a surface material comprising a print containing particles on at least one main surface of a fiber aggregate and an acrylic resin layer on the print.
A surface material that satisfies item (i) evaluated by the following measurement.
Note 1. Collect a test piece (short side: 25 cm, long side: 25 cm, thickness: 1.5 mm or more) from the surface material to be measured.
2. 2. Prepare an upper mold made by laying aluminum foil (thickness: 0.05 mm) on the main surface of a smooth plate, heat the upper mold to 120 ° C, and then put aluminum foil on the main surface of another smooth plate. Prepare a lower mold with (thickness: 0.05 mm) and heat the lower mold to 130 ° C.
3. 3. The test piece is sandwiched between the upper and lower molds with the aluminum foil surfaces facing each other. At this time, the main surface of the test piece on the side where the print exists (hereinafter referred to as the print side main surface) and the upper surface. Facing the aluminum foil surfaces in the mold,
4. Using the upper and lower molds, apply a pressure of 1 kgf / cm ^{2 on} the entire surface of one main surface of the test piece from one main surface to the other main surface for 13 seconds to apply the test piece. Press,
5. After releasing the action of pressure by the upper and lower molds and taking out the test piece from between the upper and lower molds, cool the upper mold to 20 ° C.
6. Observe the aluminum foil portion of the upper mold that was in contact with the printed side main surface of the test piece after cooling, and evaluate the following item (i).
Item (i): The resin constituting the print-side main surface of the test piece does not exist in the aluminum foil portion of the upper mold that was in contact with the print-side main surface of the test piece. "

As a result of continued examination by the applicant of the present application, a surface material "having a print containing particles on at least one main surface of the fiber aggregate and having an acrylic resin layer on the print" was heat-molded. We have found that the above-mentioned problems that occur in the interior materials and exterior materials prepared in the above-mentioned methods can be suppressed by using a surface material that satisfies the item (i) evaluated in the measurement according to the present invention. It was.
The reason for this has not been completely clarified, but it is considered that the acrylic resin layer constituting the surface material is involved in the occurrence of the above-mentioned problem.

That is, when the surface material is provided with an acrylic resin layer that easily adheres to the mold when the surface material is sandwiched between the molds and heat-molded, the acrylic resin layer is particularly easy to adhere to the mold. When the surface material has an acrylic resin layer that is peeled off and remains in the mold, the interior material and exterior material prepared by heat-molding such a surface material are intended for the main surface derived from the acrylic resin layer. There are irregularities that do not exist. In addition, particles contained in the print may fall off from the portion where the acrylic resin has peeled off.
Based on the above findings, it can be said that the measurement defined by the present invention reproduces a situation in which a surface material is simulated by being sandwiched between molds and heat-molded. It can be said that the surface material satisfying the item (i) evaluated in the measurement has an acrylic resin layer that does not easily adhere to the mold even when the surface material is sandwiched between the molds and heat-molded.
Therefore, it is possible to prevent the above-mentioned problem from occurring by a surface material that satisfies the item (i) evaluated in the measurement according to the present invention.

Further, since the surface material satisfying the configuration according to the present invention is a surface material having an acrylic resin layer that does not easily adhere to the mold, it also exhibits a secondary effect that it can be easily taken out from the mold after heat molding. It is a surface material that can be made.

It is a schematic cross-sectional view of the surface material which concerns on this invention. The pattern of the printing liquid given in the examples and the printing pattern derived from the printing liquid, the black part in the drawing is the part where the printing liquid or the print exists. Another pattern of the printing liquid given in the examples and another printing pattern derived from the printing liquid, the black portion in the drawing is the printing liquid or the portion where the print exists.

In the present invention, various configurations such as the following configurations can be appropriately selected. Further, the various lower limit values and the upper limit values to be exemplified can be arbitrarily combined as desired.

The surface material according to the present invention will be described with reference to FIG. 1, which is a schematic cross-sectional view thereof. The surface material (10) has a print (2) containing particles on one main surface of the fiber aggregate (1), and an acrylic resin layer (3) is formed on the print (2). I have.
In addition, although FIG. 1 illustrates an embodiment in which one type of print (2) exists (solid prints) on all of the fiber aggregates (1) on one main surface.
A mode in which a plurality of types of prints (2) are solidly printed on all of the fiber aggregates (1) on one main surface.
A mode in which one type of print (2) is partially present (the pattern is printed) on one main surface of the fiber aggregate (1).
A mode in which a plurality of types of prints (2) are partially present on one main surface of the fiber aggregate (1) (many types of patterns are printed).
It may be.
As shown in FIG. 1, the main surface of the surface material (10) on the upward side on the paper surface is the main surface on the side where the print (2) is present (the main surface on the print side) or an acrylic type. It may be referred to as the main surface on the resin layer (3) side.

The fiber aggregate referred to in the present invention is, for example, a fiber web, a non-woven fabric, or a sheet-like cloth such as a woven fabric or a knitted fabric. The surface material of the present invention is flexible because it contains a fiber aggregate (particularly, a non-woven fabric), and by giving a person a feeling of resistance and sliminess, it becomes a surface material having a higher moist feeling and a more excellent tactile sensation. .. In addition, the surface material provided with the fiber aggregate (particularly non-woven fabric) in which all the constituent fibers are randomly entangled is more flexible and gives a feeling of resistance and sliminess to the person, so that the feeling of moistness is high. It is preferable because it has an even better tactile sensation.
Further, since the surface material of the present invention contains a fiber aggregate, it is flexible and has excellent followability to a mold. In particular, it is preferable that the fiber aggregate constituting the surface material of the present invention is a non-woven fabric (particularly, a non-woven fabric in which all the constituent fibers are randomly entangled), which is more flexible and has excellent followability to a mold.

The constituent fibers of the fiber aggregate include, for example, a polyolefin resin (for example, polyethylene, polypropylene, polymethylpentene, a polyolefin resin having a structure in which a part of hydrocarbon is replaced with a cyano group or a halogen such as fluorine or chlorine), styrene, etc. Based resin, polyvinyl alcohol based resin, polyether resin (for example, polyether ether ketone, polyacetal, modified polyphenylene ether, aromatic polyether ketone, etc.), polyester resin (for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene) Telephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyarylate, total aromatic polyester resin, etc.), polyimide resin, polyamideimide resin, polyamide resin (for example, aromatic polyamide resin, aromatic polyetheramide resin, etc.) Nylon resin, etc.), resin having a ditryl group (for example, polyacrylonitrile), urethane resin, epoxy resin, polysulfone resin (for example, polysulfone, polyethersulfone, etc.), fluororesin (for example, polytetrafluoro) Polyacrylonitrile resin obtained by copolymerizing ethylene, polyvinylidene fluoride, etc.), cellulose resin, polybenzoimidazole resin, acrylic resin (for example, acrylic acid ester or methacrylate ester, etc.), acrylonitrile and vinyl chloride or vinylidene chloride. It can be constructed by using a known organic resin such as modern modal acrylic resin).

These organic resins may be made of either a linear polymer or a branched polymer, the organic resin may be a block copolymer or a random copolymer, and the three-dimensional structure and crystals of the organic resin may be used. The presence or absence of sex is not particularly limited. Further, it may be a mixture of a multi-component organic resin. Further, it may be a fiber prepared by kneading a pigment or a dyed fiber such as a dyed fiber.

When the surface material is required to be flame-retardant, it is preferable that the constituent fibers of the fiber aggregate contain a flame-retardant organic resin. As such a flame-retardant organic resin, for example, a moda acrylic resin, a vinylidene resin, a polyvinyl chloride resin, a polyvinylidene fluoride resin, a novoloid resin, a polyclar resin, a polyester resin obtained by copolymerizing a phosphorus compound, and a halogen-containing monomer are copolymerized. Examples thereof include acrylic resins, aramid resins, and resins kneaded with halogen-based, phosphorus-based, or metal compound-based flame retardants. Further, the surface material may be a surface material carrying a flame retardant by using a binder or the like.

The constituent fibers include, for example, melt spinning method, dry spinning method, wet spinning method, direct spinning method (melt blow method, spun bond method, electrostatic spinning method, etc.), and by removing one or more kinds of resin components from the composite fiber. It can be obtained by a known method such as a method of extracting fibers having a small fiber diameter or a method of beating the fibers to obtain divided fibers.

The constituent fibers may be composed of one type of organic resin or may be composed of a plurality of types of organic resins. As the fiber composed of a plurality of types of organic resins, it can be generally referred to as a composite fiber, for example, a core sheath type, a sea island type, a side-by-side type, an orange type, a bimetal type, or the like.

Further, the constituent fibers may include irregular cross-section fibers in addition to substantially circular fibers and elliptical fibers. In addition, as the irregular cross-sectional fiber, a polygonal shape such as a hollow shape or a triangular shape, an alphabetic character shape such as a Y shape, an irregular shape, a multi-leaf shape, a symbolic shape such as an asterisk shape, or a plurality of these shapes It may be a fiber having a fiber cross section such as a bonded shape.

When the fiber aggregate contains heat-sealing fibers as constituent fibers, the fibers are heat-sealed to each other to impart strength and morphological stability to the fiber aggregates and suppress fluffing and fiber scattering. It is preferable. Such a heat-fusing fiber may be a fully-fusing type heat-sealing fiber, or a partially-fusing type heat-sealing fiber having an embodiment such as the composite fiber described above. Is also good. As a component that exhibits heat-sealing properties in the heat-sealing fiber, for example, a heat-sealing fiber containing a low-melting-melt polyolefin resin or a low-melting polyester resin can be appropriately selected and used.

When the fiber aggregate contains crimpable fibers, the elasticity is increased and the followability to the mold is excellent, which is preferable. As such a crimpable fiber, for example, a crimpable fiber that expresses the crimp of a latent crimpable fiber, a fiber having a crimp, or the like can be used. In addition, it may contain latent crimpable fibers that develop crimping when the fiber aggregate is heated.

When the fiber aggregate is a fiber web or a non-woven fabric, for example, a dry method in which the fibers are entangled by using the above-mentioned fibers in a card device or an air array device, or the fibers are dispersed in a solvent and the fibers are entangled in a sheet shape. Wet method, direct spinning method (melt blow method, spunbond method, electrostatic spinning method, method of discharging a spinning stock solution and a gas flow in parallel to spin (for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-287138), etc.) It can be prepared by a method of spinning a fiber and collecting the fiber using the above.

The constituent fibers of the prepared fiber web can be entangled and / or integrated to prepare a non-woven fabric. As a method of entwining and / or integrating the constituent fibers with each other, for example, a method of entwining with a needle or a water stream, a method of subjecting a fiber web to a heat treatment, etc. Examples include a method of integrating.

The method of heat treatment can be appropriately selected. For example, a method of heating or heating and pressurizing with a roll, a method of heating by using a heater such as an oven dryer, a far-infrared heater, a dry heat dryer, or a hot air dryer, and infrared rays under no pressure. A method of heating the contained organic resin by irradiating with the above can be used.

The type of binder that can be used is appropriately selected, and for example, polyolefins (modified polyolefins, etc.), ethylene vinyl alcohol copolymers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, various rubbers, and derivatives thereof ( Styrene-butadiene rubber (SBR), fluororubber, urethane rubber, ethylene-propylene-diene rubber (EPDM), etc.), cellulose derivatives (carboxymethyl cellulose (CMC), hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyvinyl alcohol (PVA), polyvinyl Butyral (PVB), polyvinylpyrrolidone (PVP), polyurethane, epoxy resin, polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), acrylic resin and the like can be used.
When the binder contains an acrylic resin, it softens appropriately during thermoforming such as heat pressing using a mold, so that it is preferable to provide a surface material having excellent followability to the mold.
In addition to the above-mentioned resins, the binder may contain additives such as flame retardants, fragrances, pigments, antibacterial agents, fungicides, photocatalytic particles, emulsifiers, dispersants, and surfactants.

The basis weight of the binder contained in the fiber aggregate is appropriately selected. Specifically, the basis weight of the binder can be ² g / m ² or more. Further, the basis weight of the binder can be 50 g / m ² or less, 30 g / m ² or less, and 20 g / m ² or less.

When the fiber aggregate is a woven fabric or knitted fabric, the woven fabric or knitted fabric can be prepared by weaving or knitting the fibers prepared as described above.
In addition to the fiber web, a fiber aggregate such as a non-woven fabric, a woven fabric, or a knit may be used for the method of entwining and / or integrating the constituent fibers described above.

The fineness of the constituent fibers of the fiber aggregate is not particularly limited, but can be 1 dtex or more, 1.5 dtex or more, and 2 dtex or more so as to provide a surface material having excellent rigidity. be able to. On the other hand, it can be 100 dtex or less, 50 dtex or less, 30 dtex or less, and 10 dtex or less so that an interior material having an excellent texture can be prepared as a surface material.

Further, the fiber length of the constituent fibers of the fiber aggregate is not particularly limited, but from the viewpoint of rigidity, it can be 20 mm or more, 25 mm or more, and 30 mm or more. On the other hand, if the fiber length exceeds 110 mm, fiber lumps tend to be formed during the preparation of the fiber aggregate, which may make it difficult to provide a surface material having an excellent texture. Therefore, the fiber length can be 110 mm or less. , 60 mm or less. The "fiber length" refers to a value measured according to JIS L1015 (2010), 8.4.1c) direct method (C method).

The composition of the fiber aggregate, for example, the thickness and the basis weight, is not particularly limited and is appropriately adjusted.
The thickness of the fiber assembly can be 0.5-5 mm, 1-3 mm, 1.1-1.9 mm. In the present invention, the thickness means the length in the vertical direction when a compressive load of 20 g / cm ² is applied in the direction perpendicular to the main surface.
The basis weight of the fiber aggregate can be, for example, 50 to 500 g / m ² , 80 to 300 g / m ² , and 100 to 250 g / m ² . In the present invention, the basis weight means the mass per 1 m ^{2 on the} surface (main surface) having the widest area of the object to be measured.

The print in the present invention refers to a resin-containing layer existing on at least one main surface of the fiber assembly. Further, in the surface material of the present invention, the print contains particles. The resin constituting the print is a resin capable of supporting particles on at least one main surface of the fiber aggregate, and a resin similar to the above-mentioned binder can be adopted. In particular, since it is moderately softened during thermoforming such as heat pressing using a mold, it is possible to provide a surface material having excellent followability to the mold. Therefore, the resin constituting the print contains an acrylic resin. It is preferable that the resin constituting the print is only an acrylic resin.

In addition to the resin, the print may contain additives such as flame retardants, fragrances, pigments, antibacterial agents, fungicides, photocatalytic particles, emulsifiers, dispersants, surfactants, and thickeners. Good.

Further, the mode of printing existing on one main surface of the fiber aggregate can be appropriately selected, and the mode existing so as to cover the entire surface of the main surface, a pattern having a pattern such as a grid pattern, a linear pattern, or a dot shape. Alternatively, it may be a mode in which a part of the main surface is covered and exists so as to form a handle having an indefinite shape or the like. Further, the print may be provided with a layer containing one type of resin, or may be provided with a plurality of layers containing one type or a plurality of types of resin, and specifically, the handle, the resin, and the inclusions are the same. Alternatively, a plurality of different prints may be provided.
The print may be present on both main surfaces of the fiber aggregate as long as it is present on one main surface of the fiber aggregate. In addition to the mode in which the print exists only on the main surface of the fiber aggregate, a part of the components (resin, etc.) constituting the print penetrates between the constituent fibers constituting the fiber aggregate. You may.

The basis weight of the print suitably selected but, for example, be a 2 to 50 g / ^{m 2,} can be 10 to 30 g / ^{m 2.}

The average particle size of the particles included in the surface material of the present invention is appropriately adjusted so as to provide a surface material having excellent tactile sensation, but the average particle size of the particles is preferably 14 μm to 160 μm, preferably 30 μm to 50 μm. preferable.
In the present invention, the average particle size of particles refers to a value calculated by the following method.
(Calculation method of average particle size)
(1) Take a 200x optical micrograph of a plurality of particles placed in a room temperature (25 ° C.) atmosphere, or 200x optical magnification of both main surfaces of a surface material placed in a room temperature (25 ° C.) atmosphere. Take each micrograph.
(2) Ten particles are randomly selected from the photographs in which the presence of particles is confirmed.
(3) The particle diameters of the 10 selected particles are calculated, and the average value of the calculated values is taken as the average particle diameter. The diameter of a circle having the same area as the area of the particles shown in the photograph is calculated, and the value of the diameter is regarded as the particle diameter of the particles.

The coefficient of variation in the particle size of the particles contained in the print (hereinafter, may be abbreviated as CV value) can be appropriately selected, but the smaller the CV value, the narrower the distribution of the particles, and the more excellent the tactile sensation is on the surface. The material can be provided efficiently as intended. Therefore, the CV value in the particle size of the particles is preferably 17% or less, and preferably 16% or less. The lower limit of the average particle size can be appropriately selected, but ideally it is 0%.

The type of particles included in the surface material according to the present invention can be appropriately selected, and may be solid particles or hollow particles. However, since it is easy to provide a surface material having an improved tactile sensation, hollow particles are adopted. Is preferable. Further, the constituent components of the particles can be appropriately selected. For example, inorganic particles composed of an inorganic component such as silica or alumina, organic particles composed of an organic resin, or particles having a composition containing an organic resin and an inorganic component. It may be.
When the particles are hollow particles, it is preferable that the components constituting the hollow particles contain an organic resin so that the particles are easily deformed in the particle diameter direction.

The hollow particle in the present invention means a particle having a cavity inside. Since hollow particles are more easily deformed in the particle diameter direction than solid particles, when a person touches the main surface of a surface material containing hollow particles, the person feels elasticity rather than the touch when touching a hard object. Feel the tactile sensation when you touch what you have. As a result, it is preferable to provide a surface material having an improved tactile sensation because the flexibility is easily felt when the main surface of the surface material is touched. In particular, since the flexible hollow particles make it easy to realize a surface material having an excellent tactile sensation, and because the print becomes three-dimensional and it is easy to realize a surface material having an excellent design, the particles that foam when heated are formed. It is preferable that the surface material has hollow particles formed by foaming.

The mode in which the print contains particles can be appropriately selected, and the particles are present only on the exposed main surface of the print, or the particles are present inside the print and on the exposed main surface. It can be an embodiment.
As a mode in which the particles are present on the exposed main surface of the print, for example, the particles are adhesively supported on the exposed main surface of the print by a resin, or the particles are supported on the exposed main surface of the print. It can be a mode in which a part is sunk and supported. Then, a part of the particles can be exposed on the main surface of the print.

The amount of particles contained in the print can be appropriately selected, but can be 15 g / m ² or less, 12 g / m ² or less, and 9 g / m ² or less. On the other hand, the lower limit value of the content is appropriately adjusted, so that it can provide a surface material having a characteristic according to the present invention is preferably greater than 0.1 g / m ^2, greater than 0.3 g / m ² Is preferable.

In addition to the resin and particles, the print contains additives such as flame retardants, fragrances, pigments, antibacterial agents, fungicides, photocatalytic particles, emulsifiers, dispersants, surfactants, and thickeners. You may.

The print may contain a large number of types of particles, but the particles have the above-mentioned configuration so as to provide a surface material having a higher tactile sensation such as a high moist feeling by giving a feeling of resistance and sliminess. A surface material having a print containing only hollow particles is preferable. In particular, a surface material having a print containing only one type of hollow particles is more preferable so that a surface material in which the above-mentioned effects can be efficiently exhibited can be provided.

The percentage of the solid content mass of the particles to the solid content mass of the resin constituting the print can be appropriately adjusted, but can be 6% by mass to 400% by mass, 12% by mass to 200% by mass, 24. It can be from% to 100% by mass.
The percentage of the solid content mass of the particles to the solid content mass of the resin constituting the print can be calculated by rounding off the decimal point of the value calculated by the following method.
A = 100 x B / C
A: Percentage of the solid content of particles to the solid content of the resin that makes up the print (unit: mass%)
B: Solid mass of particles constituting the print (unit: g / m ² )
C: Solid content mass of the resin constituting the print (unit: g / m ² )
Further, when it is difficult to measure the solid content mass of the particles and the resin constituting the print provided by the surface material, one of the fiber aggregates is used to form the print in the surface material manufacturing process. By substituting the solid content mass of the particles given on the main surface of the above into the above formula as B and substituting the solid content mass of the resin as C into the above formula, the solid content mass of the resin constituting the print is substituted. Calculate the percentage (unit: mass%) of the solid content mass of the particles with respect to. Alternatively, the solid content mass of the particles in the coating liquid containing the particles constituting the print and the resin, which is applied on one main surface of the fiber aggregate to form the print in the process of manufacturing the surface material, is described above as B. By substituting into the above formula with the solid content mass of the resin as C, the percentage (unit: mass%) of the solid content mass of the particles with respect to the solid content mass of the resin constituting the print is calculated. ..

The surface material of the present invention includes a print containing particles on one main surface of the fiber aggregate and a main on the print (in the print provided by the surface material, the side opposite to the side where the fiber aggregate exists). An acrylic resin layer is provided on the surface).

In the acrylic resin layer, particles fall off from the print of the surface material, and / or particles fall off from the interior material or exterior material formed by molding the surface material (particles fall off from the part derived from the print of the surface material). It is a layer that plays a role in preventing (doing). The acrylic resin layer may contain any of the other organic resins described above as long as it contains an acrylic resin, but the acrylic resin so that the surface material according to the present invention can effectively exert its function. It is preferable that the organic resin constituting the layer is only an acrylic resin.

Even if the acrylic resin layer contains other additives such as flame retardants, fragrances, pigments, antibacterial agents, fungicides, photocatalytic particles, emulsifiers, dispersants, surfactants, and thickeners. Good.

In addition, although the mode of existence of the acrylic resin layer can be appropriately selected, the entire surface of the main surface opposite to the side where the fiber aggregate exists in the printing of the surface material (on the printing) so as to maximize the above-mentioned effect can be selected. It is preferable that the embodiment is present so as to cover the entire surface). In addition to the mode in which the acrylic resin layer exists only on the print, the acrylic resin layer may have a mode in which it penetrates between the constituent fibers constituting the print or the fiber aggregate.

It is desirable that the surface material includes a resin layer composed of only an acrylic resin as an acrylic resin layer so that the surface material according to the present invention can effectively exert its function.
Basis weight of the acrylic resin layer is appropriately selected, but can basis weight of the acrylic resin layer is 2~80g / ^{m 2,} can be a 5 to 70 g / ^{m 2,} in 12~55g / ^{m 2} There can be.

The surface material according to the present invention satisfies the item (i) evaluated by the following measurement.
1. 1. A test piece (short side: 25 cm, long side: 25 cm, thickness: 1.5 mm or more) is collected from the surface material to be measured.
2. 2. Prepare an upper mold made by laying aluminum foil (thickness: 0.05 mm) on the main surface of a smooth plate, heat the upper mold to 120 ° C, and then put aluminum foil on the main surface of another smooth plate. Prepare a lower mold on which (thickness: 0.05 mm) is laid, and heat the lower mold to 130 ° C.
3. 3. The test piece is sandwiched between the upper and lower molds with the aluminum foil surfaces facing each other. At this time, the main surface of the test piece on the side where the print exists (hereinafter referred to as the print side main surface) and the upper surface. Face the aluminum foil surfaces on the mold.
4. Using the upper and lower molds, apply a pressure of 1 kgf / cm ^{2 on} the entire surface of one main surface of the test piece from one main surface to the other main surface for 13 seconds to apply the test piece. Press.
5. After releasing the action of pressure by the upper mold and the lower mold and taking out the test piece from between the upper mold and the lower mold, the upper mold is cooled to 20 ° C.
6. Observe the aluminum foil portion in contact with the printed side main surface of the test piece in the upper mold after cooling, and evaluate the following item (i).
Item (i): The resin constituting the printed side main surface of the test piece is not present in the aluminum foil portion of the upper mold that was in contact with the printed side main surface of the test piece.

Further, in the above measurement, the aluminum foil portion of the upper mold that was in contact with the printed side main surface of the test piece in the upper mold after cooling was observed, and the surface material satisfies the following item (ii). Is more preferable.
Item (ii): Acrylic resin and hollow particles are not present in the aluminum foil portion of the upper mold that was in contact with the main surface of the test piece on the print side.

The surface material satisfying the item (i) or the item (ii) evaluated by the above-mentioned measurement can be realized by specifically selecting the type of the acrylic resin constituting the acrylic resin layer.

The applicant of the present application shall adopt an acrylic resin satisfying the items (iii) and (iv) evaluated in the following (evaluation method of acrylic resin) as the acrylic resin constituting the acrylic resin layer. It was found that the surface material according to the present invention (a surface material satisfying the item (i) or item (ii) evaluated by the above-mentioned measurement) can be realized.
(Evaluation method for acrylic resin)
1. 1. Prepare a test piece made of acrylic resin (short side: 5 cm, long side: 7 cm, thickness: 2 mm).
2. 2. The test piece is allowed to stand in an atmosphere of 160 ° C. for 20 minutes to heat the test piece.
3. An aluminum foil (thickness: 0.05 mm) is laid on the main surface of a smooth plate heated to 140 ° C., and the heated test piece is laminated on the main surface of the aluminum foil. At this time, the main surface of the aluminum foil and the main surface of the heated test piece are brought into contact with each other and laminated.
4. From the exposed main surface side of the test piece toward the thickness direction of the test piece, the pressure plate is pressed against the entire surface of the main surface at a pressure of 50 kgf / cm ² for 3 minutes, and then the pressure plate is pressed. The test piece is cooled to 20 ° C. apart from the test piece.
5. The state of the test piece after being pressed is evaluated by the following two items (iii) and (iv).
Item (iii): No waviness is generated on the exposed main surface of the test piece after the press, or the height of the waviness generated is less than 2 mm.
Item (iv): The size of the test piece after the pressing is 6 cm or less on the short side and 8 cm or less on the long side.

As a result of continued examination by the applicant of the present application, a surface material satisfying the item (i) or item (ii) evaluated by the above-mentioned measurement is sandwiched between molds and heat-molded when preparing the interior material and the exterior material. , It was found that the acrylic resin layer in contact with the mold can be realized because it is difficult to flow unintentionally. That is, by providing an acrylic resin layer containing an acrylic resin having low fluidity when the surface material is heated, the surface material is sandwiched between molds and heat-molded to form an interior material or an exterior material. Can occur when preparing
-The problem that there are unintended irregularities on the main surface derived from the acrylic resin layer,
-The problem that particles contained in the print may fall off from the main surface side derived from the acrylic resin layer.
It was found that the occurrence of

When the print contains particles (particularly foamed hollow particles), the strength of the print is weaker than that when the print does not contain particles. Therefore, when a surface material having a print containing particles (particularly foamed hollow particles) is sandwiched between molds and heat-molded to prepare an interior material or an exterior material, the above-mentioned problems are more likely to occur in the prepared interior material or exterior material. It tends to occur easily.
However, when the surface material according to the present invention includes, in particular, an acrylic resin satisfying the items (iii) and (iv) evaluated in the above-mentioned (evaluation method for acrylic resin) in the acrylic resin layer. It is possible to effectively prevent the above-mentioned problems from occurring.

The surface roughness (SMD) and average friction coefficient (MIU) of the main surface of the surface material of the present invention on the side where the print is present are appropriately adjusted so as to realize a surface material having an excellent tactile sensation.
The surface roughness (SMD; surface loadness) is a value measured using a surface tester (KES-FB4, manufactured by Kato Tech Co., Ltd.), and 400 g of a surface material sample (20 cm square) is used as a tester. The sample was set by applying a load, and the roughness contactor (0.5 mm wire, contact surface width: 5 mm) was brought into contact with the sample by applying a load of 10.0 g to bring the sample to 1 mm / sec. It means the average deviation (average development of surface roughness data) of the surface unevenness data measured by moving at the speed of, and the unit is μm.

Surface roughness is literally an index showing the unevenness on the main surface, that is, the smoothness of the main surface. The larger the surface roughness (SMD) value, the smaller the gap tends to be, and it is easier to provide a surface material having excellent design and tactile sensation. Therefore, the surface roughness (SMD) is 2.75 μm or more. Is preferable. The upper limit of the surface roughness (SMD) is not particularly limited. However, when the surface roughness (SMD) is excessively high, a new gap is created between the tactile sensation planted by the illusion and unconsciously imagined and the tactile sensation actually touched on the main surface. The surface roughness (SMD) is preferably 10.0 μm or less because there is a risk of this.

The coefficient of average friction (MIU) is an indicator of the flexibility of the main surface. The average friction coefficient (MIU) is an average value (average value of μ in a distance of 20 mm) between 20 mm of μ (friction coefficient) measured using a surface tester (KES-FB4). Yes, a sample of surface material (20 cm square) was set on a testing machine with a load of 400 g, and a friction element (5 mm × 5 mm) was brought into contact with the sample by applying a load of 50 g to bring the sample to 1 mm / sec. It means the average value measured by moving at the speed of.
The higher the average coefficient of friction (MIU) of the main surface of the surface material on the side where the print is present, the more flexible the main surface tends to be and the better the tactile sensation. ) Is preferably 0.15 or more, preferably 0.20 or more, and more preferably 0.25 or more. On the other hand, if the value of the average coefficient of friction (MIU) is too large, the frictional resistance is too strong and the tactile sensation may be impaired. Therefore, the value is preferably 1.6 or less.

The thickness of the surface material is appropriately selected, but can be 2.5 mm or less and 2.0 mm or less. On the other hand, the lower limit of the thickness is adjusted as appropriate, but it is realistic that it is 0.5 mm or more.
The basis weight of the surface material is appropriately selected, but it can be 300 g / m ² or less. On the other hand, the lower limit of the basis weight is adjusted as appropriate, but it is realistic that it is 100 g / m ² or more.

The surface material of the present invention may further include other constituent members such as a porous body, a film, and a foam. These constituent members can be provided by being laminated on the main surface side of the surface material, which is different from the main surface on the acrylic resin layer side.

Next, the method for producing the surface material of the present invention will be described. The points having the same configuration as the items described for the surface material described above will be omitted.
The method for producing the surface material according to the present invention can be appropriately selected, but as an example,
(1) Step of preparing fiber aggregate,
(2) A step of preparing a printing liquid by mixing a resin and particles that can form a print with a solvent or a dispersion medium.
(3) A step of applying a printing liquid onto at least one main surface of the fiber aggregate,
(4) A step of preparing a fiber aggregate having a print by removing a solvent or a dispersion medium by heating the fiber aggregate to which the printing liquid is applied.
(5) A component containing an organic resin (acrylic resin or acrylic resin and other resin) capable of forming an acrylic resin layer is mixed with a solvent or a dispersion medium to prepare an acrylic resin layer coating liquid. Process to do,
(6) A step of applying an acrylic resin layer coating liquid on the main surface on the print side of the fiber assembly including the print.
(7) A step of preparing a surface material by removing a solvent or a dispersion medium by heating a fiber aggregate having a print to which an acrylic resin layer coating liquid is applied.
A method for producing a surface material, which comprises the above.

Step (1) will be described.
As the fiber aggregate, for example, a fiber web, a non-woven fabric, or a sheet-like cloth such as a woven fabric or a knitted fabric is prepared. As the fineness and fiber length of the constituent fibers in the fiber aggregate, and the thickness and basis weight of the fiber aggregate, those having the above-mentioned numerical values can be adopted.

Step (2) will be described.
The type of solvent or dispersion medium can be appropriately selected, but the resin that can form the print is dissolved and the particles can be dispersed without being dissolved so that the printing liquid can be suitably applied onto one main surface of the fiber aggregate. It is preferable to use a solvent, or to use resin particles that can form a print and a dispersion medium in which the particles are not dissolved and can be dispersed. In addition to particles, additives such as flame retardants, fragrances, pigments, antibacterial agents, fungicides, photocatalytic particles, emulsifiers, dispersants, surfactants, and thickeners are dissolved or dispersed in the printing liquid. And may be contained. The type of particles can be appropriately selected, but for the reasons described above, the particles are preferably heated and foamed.

The step (3) will be described.
The method of applying the printing liquid on one main surface of the fiber assembly can be appropriately selected, but the printing liquid is applied to one main surface of the fiber assembly as it is or in a foamed state, using a spray or an impregnating roll. A method of spraying or applying the fibers, a method of immersing one main surface of the fiber aggregate in the printing liquid, or the like can be adopted. The mode of the printing liquid to be applied onto one main surface of the fiber aggregate can be appropriately selected, but a method of applying so as to cover the entire main surface, printing or printing so as to form a pattern on the main surface You can select the method of granting. In addition, one kind of printing liquid may be given, or a plurality of kinds of printing liquids may be given. Further, when a plurality of types of printing liquids are applied, the application mode (pattern, composition of the printing liquid) of each printing liquid may be different.

Step (4) will be described.
A method for preparing a fiber aggregate having a print by removing a solvent or a dispersion medium can be appropriately selected, and for example, it is heated by being subjected to a heater such as an oven dryer, a far-infrared heater, a dry heat dryer, or a hot air dryer. The solvent or dispersion medium can be evaporated and removed by allowing it to stand in a room temperature atmosphere or a reduced pressure atmosphere. The heating temperature at which the solvent or dispersion medium is removed is a temperature at which the solvent or dispersion medium can volatilize, and the shape and function of constituent members such as fiber aggregates and hollow particles are not unintentionally lowered. Select the upper limit of the heating temperature.
When the fiber aggregate is a fiber web, the constituent fibers are bonded to each other by this step (bonding with a molten binder or melting and adhering a thermoplastic component contained in the constituent fibers) to form a non-woven fabric. May be formed.
Further, when the particles are provided with particles that are heated and foamed, the particles may be foamed by this step.

The step (5) will be described.
The type of solvent or dispersion medium can be appropriately selected, but the organic resin that can form the acrylic resin layer is dissolved and the fiber aggregates and components of the print are not dissolved so that the acrylic resin layer coating liquid can be preferably applied. It is preferable to use a solvent or a dispersion medium, or an organic resin capable of forming an acrylic resin layer, and a solvent or a dispersion medium in which the constituent components of the fiber aggregate and the print are not dissolved. Further, the above-mentioned additives may be dissolved or dispersed in the acrylic resin layer coating liquid and contained.

Step (6) will be described.
The method of applying the acrylic resin layer coating liquid on the main surface of the fiber assembly provided with the print on the print side can be appropriately selected, and for example, the means described in the step (3) can be adopted.
One type of acrylic resin layer coating liquid may be applied, or a plurality of types of acrylic resin layer coating liquid may be applied. Further, when a plurality of types of acrylic resin layer coating liquids are applied, the application mode (pattern, composition of the acrylic resin layer coating liquid) of each acrylic resin layer coating liquid may be different.

Step (7) will be described.
The method for preparing the surface material by removing the solvent or the dispersion medium can be appropriately selected, and for example, the means mentioned in the step (4) can be adopted.

By using the above-mentioned production method, the surface material according to the present invention can be produced.
In the above-mentioned method for manufacturing a surface material, there are various steps such as a step of laminating other constituent members such as a porous body, a film, and a foam, and a step of punching a shape according to an application and a mode of use. It may be a method of manufacturing a surface material including the next step.
It should be noted that these constituent members can be provided by being laminated on the main surface side of the surface material, which is different from the main surface on the acrylic resin layer side.
Further, it may be subjected to a pressure treatment step for smoothing the surface, such as a Reliant press treatment.

Hereinafter, the present invention will be specifically described with reference to Examples, but these do not limit the scope of the present invention.

(Preparation of fiber aggregate)
Using 100% of the original polyester fiber (fineness: 2.2 dtex, fiber length: 38 mm), the fiber is opened by a card machine to form a fiber web, and then needle punching is performed from one side at a needle density of 400 lines / m ^2. After that, a needle punched non-woven fabric (grain: 180 g / m ² , thickness: 1.5 mm) was prepared by subjecting the fibers between heat rolls (gap interval: 0.6 mm, roll heating temperature: 165 ° C.).
Next, from the surface opposite to the needling surface of the needle punched non-woven fabric, the binder solution blended in the ratio described below was applied in a foamed state and applied between rolls (gap interval: 0.25 mm). Then, by drying with a can dryer at a temperature of 160 ° C., a binder-bonded non-woven fabric (texture: 185 g / m ² , thickness: 1.6 mm, non-woven fabric in which all constituent fibers are randomly entangled) was prepared.
Binder solution-Acrylic acid resin binder 4 (details will be described later): 5.4 parts-Thickener: 0.2 parts-Surfactant: 1.0 parts-25% Ammonia water: 0.1 parts-Water: 93.3 copies

(Preparation of printing liquid)
Various printing liquids blended in the proportions shown in Table 1 were prepared. The hollow particles blended in the printing liquid were hollow particles composed of organic components (average particle diameter before heating: 13 μm), and were particles that foamed three times in a heating atmosphere at 160 ° C. For compositions that are not present in the printing solution, "-" is shown in the table.

(Preparation of acrylic resin layer coating liquid)
Various resin solutions blended in the proportions shown in Table 2 were prepared. When the acrylic resins constituting the acrylic resin binders 1 and 2 and the acrylic binder 5 were applied to (evaluation method of acrylic resin), both the item (iii) and the item (iv) were not satisfied. It was. On the other hand, when the acrylic resins constituting the acrylic resin binders 3 to 4 were applied to (the method for evaluating the acrylic resin), both the item (iii) and the item (iv) were satisfied. As can be seen from the difference in the glass transition temperature (Tg) and the result of applying to (evaluation method of acrylic resin), each type of acrylic resin constituting each acrylic resin binder used (for example, structure of polymer chain). , Molecular weight, etc.) are different from each other.
The "Tg (glass transition temperature)" referred to in the present invention is a DTA curve measured by subjecting a resin to be measured (an acrylic resin constituting an acrylic resin binder, etc.) to a differential thermal analyzer (DTA). The temperature at the intersection of the tangent line of the baseline and the tangent line of the steep descending position of the heat absorption region due to the glass transition.
For the composition not present in the acrylic resin layer coating liquid, "-" is described in the table.

(Reference example 1)
The printing liquid A was applied to the pattern A shown in FIG. 2 using a cylinder on the main surface of the binder-adhesive non-woven fabric to which the binder liquid was applied. Then, the printing liquid B was applied to the B pattern shown in FIG. 3 using a cylinder on the main surface on which the print derived from the printing liquid A was exposed.
Then, by drying with a dryer at a temperature of 160 ° C., an A pattern print derived from the printing liquid A and a B pattern print derived from the printing liquid B (containing foamed hollow particles) are printed on one main surface of the binder adhesive non-woven fabric. A print with a pattern in which the particles are overlapped is provided.
In this way, a surface material having a print containing hollow particles on one main surface of the binder-bonded non-woven fabric (weight: 195.0 g / m ² , basis weight of print derived from printing liquid A: 6.0 g / m). ^2. The basis weight of the print derived from the printing liquid B: 4.0 g / m ² , thickness: 1.5 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface on the side where the print was present was 6.494 μm, and the MIU was 0.243.

(Comparative Example 1)
The acrylic resin coating liquid 1 was applied (solid printing) to the entire surface of the main surface of the surface material prepared in Reference Example 1 on the side provided with the print, using a cylinder. After that, by drying with a dryer at a temperature of 140 ° C., a surface material containing hollow particles is provided on one main surface of the binder-bonded non-woven fabric, and a surface material (weighting) provided with an acrylic resin layer on the print. : 203.0g / ^{m 2,} the printing liquid a from the printed mass per unit area: 6.0g / ^{m 2,} the printing liquid B from the print basis weight: 4.0g / ^{m 2,} acrylic derived from an acrylic-based resin coating liquid 1 The basis weight of the resin layer: 8.0 g / m ² , thickness: 1.6 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 6.039 μm, and the MIU was 0.215.

(Comparative Example 2)
Similar to Comparative Example 1, a print containing hollow particles is provided on one main surface of the binder-adhesive non-woven fabric except that the acrylic resin coating liquid 2 is used instead of the acrylic resin coating liquid 1. At the same time, a surface material having an acrylic resin layer on the print (grain: 203.0 g / m ² , print grain derived from printing liquid A: 6.0 g / m ² , print grain derived from printing liquid B: 4.0 g / m ² , the texture of the acrylic resin layer derived from the acrylic resin coating liquid 2: 8.0 g / m ² , thickness: 1.6 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 6.082 μm, and the MIU was 0.270.

(Example 1)
Similar to Comparative Example 1, a print containing hollow particles is provided on one main surface of the binder-adhesive non-woven fabric except that the acrylic resin coating liquid 3 is used instead of the acrylic resin coating liquid 1. At the same time, a surface material having an acrylic resin layer on the print (grain: 203.0 g / m ² , print grain derived from printing liquid A: 6.0 g / m ² , print grain derived from printing liquid B: 4.0 g / m ² , the texture of the acrylic resin layer derived from the acrylic resin coating liquid 3: 8.0 g / m ² , thickness: 1.6 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 6.164 μm, and the MIU was 0.218.

(Example 2)
Similar to Comparative Example 1, a print containing hollow particles is provided on one main surface of the binder-adhesive non-woven fabric except that the acrylic resin coating liquid 4 is used instead of the acrylic resin coating liquid 1. At the same time, a surface material having an acrylic resin layer on the print (grain: 203.0 g / m ² , print grain derived from printing liquid A: 6.0 g / m ² , print grain derived from printing liquid B: 4.0 g / m ² , the texture of the acrylic resin layer derived from the acrylic resin coating liquid 4: 8.0 g / m ² , thickness: 1.6 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 5.957 μm, and the MIU was 0.267.

(Example 3)
Similar to Example 2, a print containing hollow particles is provided on one main surface of the binder adhesive nonwoven fabric except that the amount of the printing liquid B applied is increased, and an acrylic resin is provided on the print. Surface material with layers (weight: 206.0 g / m ² , print grain derived from print liquid A: 6.0 g / m ² , print grain derived from print liquid B: 7.0 g / m ² , acrylic type The basis weight of the acrylic resin layer derived from the resin coating liquid 4: 8.0 g / m ² , thickness: 1.7 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 6.944 μm, and the MIU was 0.214.

(Comparative Example 3)
Similar to Comparative Example 1, a print containing hollow particles is provided on one main surface of the binder-adhesive non-woven fabric except that the acrylic resin coating liquid 5 is used instead of the acrylic resin coating liquid 1. At the same time, a surface material having an acrylic resin layer on the print (grain: 203.0 g / m ² , print grain derived from printing liquid A: 6.0 g / m ² , print grain derived from printing liquid B: 4.0 g / m ² , the texture of the acrylic resin layer derived from the acrylic resin coating liquid 5: 8.0 g / m ² , thickness: 1.6 mm) was prepared.
In the surface material prepared in this manner, the SMD of the main surface (acrylic resin layer) on the side where the print was present was 6.144 μm, and the MIU was 0.213.

The surface materials prepared as described above were evaluated by measuring various physical properties and summarized in Table 3. Regarding the items (i) and item (ii) described above, "○" was described for the surface material satisfying the item, and "x" was described for the surface material not satisfying the item. In addition, "-" is described for the surface material that is not subject to evaluation due to its composition.

In addition, the item of (formation) was evaluated by the following method.
(Evaluation method of texture)
In the test piece after evaluating the item (i) and the item (ii), the main surface of the test piece in contact with the aluminum foil portion of the upper mold on the side where the print was present was visually observed.
As a result of observation, if print unevenness is observed on the main surface, it means that the resin layer is peeled off or the resin layer and the print are peeled off as a result of applying heating and pressurization to the surface material. Therefore, when the interior and exterior materials are prepared by sandwiching them in a mold and heating and molding, it is evaluated that it is difficult to provide the interior and exterior materials with excellent texture, and "×" in the table. Was described.
On the other hand, as a result of observation, when no print unevenness was observed on the main surface, peeling of the resin layer and peeling of the resin layer and the print occurred even if the surface material was heated and pressed. Since it means that there was no such material, it was evaluated that it is an easy surface material to provide an interior material or exterior material with excellent texture when it is sandwiched in a mold and heat-molded to prepare an interior material or exterior material. "○" is shown in the table.

From the results of comparing the Reference Example and the Comparative Example with the Examples, when the surface material is sandwiched between molds and heat-molded to prepare the interior material and the exterior material because the surface material satisfies the configuration according to the present invention. Can occur in
-The problem that there are unintended irregularities on the main surface derived from the acrylic resin layer,
-The problem that particles contained in the print may fall off from the main surface side derived from the acrylic resin layer.
It was possible to easily provide interior materials and exterior materials with excellent texture by preventing the occurrence of.

Further, by providing a surface material that satisfies the configuration according to the present invention, it is possible to provide a surface material that can exert a secondary effect of being easily taken out from the mold after heat molding.

The surface material of the present invention can be suitably used for automobiles such as ceilings, door sides, pillar garnishes, and rear packages; for interiors such as partitions; and for building materials such as wall coverings.

10: Surface material 1: Fiber aggregate 2: Particle-containing print 3: Acrylic resin layer

Claims (1)

A surface material having a print containing particles on at least one main surface of the fiber aggregate and an acrylic resin layer on the print.
A surface material that satisfies item (i) evaluated by the following measurement.
Note 1. Collect a test piece (short side: 25 cm, long side: 25 cm, thickness: 1.5 mm or more) from the surface material to be measured.
2. 2. Prepare an upper mold made by laying aluminum foil (thickness: 0.05 mm) on the main surface of a smooth plate, heat the upper mold to 120 ° C, and then put aluminum foil on the main surface of another smooth plate. Prepare a lower mold with (thickness: 0.05 mm) and heat the lower mold to 130 ° C.
3. 3. The test piece is sandwiched between the upper and lower molds with the aluminum foil surfaces facing each other. At this time, the main surface of the test piece on the side where the print exists (hereinafter referred to as the print side main surface) and the upper surface. Facing the aluminum foil surfaces in the mold,
4. Using the upper and lower molds, apply a pressure of 1 kgf / cm ^{2 on} the entire surface of one main surface of the test piece from one main surface to the other main surface for 13 seconds to apply the test piece. Press,
5. After releasing the action of pressure by the upper and lower molds and taking out the test piece from between the upper and lower molds, cool the upper mold to 20 ° C.
6. Observe the aluminum foil portion of the upper mold that was in contact with the printed side main surface of the test piece after cooling, and evaluate the following item (i).
Item (i): The resin constituting the printed side main surface of the test piece does not exist in the aluminum foil portion of the upper mold that was in contact with the printed side main surface of the test piece.

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