WO2023228486A1 - 樹脂付着繊維基材、及び、成形体の製造方法 - Google Patents
樹脂付着繊維基材、及び、成形体の製造方法 Download PDFInfo
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- WO2023228486A1 WO2023228486A1 PCT/JP2023/004557 JP2023004557W WO2023228486A1 WO 2023228486 A1 WO2023228486 A1 WO 2023228486A1 JP 2023004557 W JP2023004557 W JP 2023004557W WO 2023228486 A1 WO2023228486 A1 WO 2023228486A1
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- WIPO (PCT)
- Prior art keywords
- resin
- base material
- less
- mass
- fiber base
- Prior art date
Links
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
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- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
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- 150000003871 sulfonates Chemical class 0.000 description 1
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- 238000001721 transfer moulding Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered 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
- B32B5/22—Layered 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
- B32B5/24—Layered 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
Definitions
- One aspect of the present invention relates to a resin-attached fiber base material, a method for producing a molded article, and the like.
- the fiber-reinforced material can be used to obtain a molded article by various molding methods.
- RTM Resin transfer molding
- the fiber reinforced material may be cut, and it is required to avoid fraying of the fibers when the fiber reinforced material is cut.
- a laminate may be obtained by laminating fiber-reinforced materials.
- Such fiber-reinforced materials are required to have sufficient adhesion from the viewpoint of maintaining the shape of the laminate.
- a resin-attached fiber base material comprising a fiber base material and a dot-shaped resin portion provided on at least one surface of the fiber base material is used as the fiber reinforced material.
- the resin material matrix resin
- the resin material becomes a fiber-reinforced material. It is required to suppress the impediment to the penetration of the resin material (removal of the resin material (matrix resin)).
- One aspect of the present invention is to provide a resin-attached fiber base material that has sufficient adhesiveness, can suppress fiber fraying during cutting, and has good shedding of the resin material when brought into contact with the resin material.
- the purpose is to Another aspect of the present invention is to provide a method for manufacturing a molded article using such a resin-attached fiber base material.
- the present invention relates to the following [1] to [4].
- [1] A fiber base material and a dot-shaped resin portion provided on at least one surface of the fiber base material, the resin portion containing a thermoplastic resin, The ratio A2/A1 of the mass A2 per unit area of the resin part to the mass A1 of is 0.005 to 0.105, and the ratio of the average diameter B2 of the resin part to the average constituent unit width B1 of the fiber base material.
- a resin-attached fiber base material having a B2/B1 ratio of 0.06 to 0.96.
- a resin-attached fiber base material has sufficient adhesiveness, can suppress fiber fraying during cutting, and has good release of resin material when brought into contact with the resin material.
- a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively.
- the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.
- the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.
- “A or B” may include either A or B, or may include both.
- the resin-attached fiber base material (fiber reinforced material) includes a fiber base material and a dot-shaped resin part provided on at least one surface of the fiber base material, and the resin part is heated Contains plastic resin.
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the fiber base material is 0.005 to 0.105
- the The ratio B2/B1 of the average diameter B2 (dot diameter) of the resin portion to the average constituent unit width B1 of the base material is 0.06 to 0.96.
- the resin-attached fiber base material according to this embodiment has sufficient adhesiveness.
- the resin-attached fiber base material according to the present embodiment fraying of the fibers during cutting can be suppressed.
- the ratio of the mass of the fibers falling from the cut surface to the mass of the resin-attached fiber base material before cutting is 5. You can get less than %.
- the resin-attached fiber base material according to the present embodiment when the resin material (matrix resin for obtaining a resin molded body) is brought into contact with it, the resin material can be easily removed.
- the resin-attached fiber base material according to the present embodiment it is possible to obtain a ratio of the permeation amount M1 to the permeation amount M2 of 60% or more in the evaluation described in Examples below.
- the resin-attached fiber base material according to the present embodiment can be suitably used for manufacturing various molded bodies obtained using resin materials (for example, RTM molding).
- One aspect of the resin-attached fiber base material according to this embodiment has sufficient flexibility.
- a resin-attached fiber base material it is possible to obtain acceptable flexibility compared to the feel of a fiber base material without a resin portion in the evaluation described in Examples below.
- the fiber base material supports the resin part.
- the fiber base material may be a fibrous fabric, an orthogonal fiber nonwoven fabric, a multiaxial fiber nonwoven fabric, or a fiber knitted fabric.
- the texture of the fiber fabric is not particularly limited.
- Examples of the weave structure of the fiber fabric include a plain weave structure, a twill weave structure, a satin weave structure, a ribbed weave structure, and the like.
- the weave structure of fiber fabrics is determined from the viewpoints of easily suppressing fiber fraying, facilitating the release of the resin material (matrix resin), facilitating obtaining excellent adhesion, and obtaining excellent flexibility. , plain weave or twill weave.
- the weave structure of the fiber fabric may be a multiple weave structure such as a double weave structure (biaxial weave structure) or a triple weave structure.
- the weave structure of the fiber fabric may be a modified structure such as a plaited weave structure or a ribbed weave structure.
- the texture of the fiber fabric may be a special texture such as a patterned texture or a sand grain texture.
- the texture of the fiber fabric may be any other texture.
- the fiber base material is not limited to being composed of one type of fiber.
- the warp and weft may be composed of different types of fiber yarns.
- different types of fiber yarns may be included in some of the warp or weft yarns.
- a thermoplastic resin fiber thread made of a thermoplastic resin may be included in a part of the warp or weft of the textile fabric.
- yarns made of a resin different from thermoplastic resin and thermoplastic resin fiber yarns may be mixed, doubled, or twisted together.
- the fiber base material may contain inorganic fibers or organic fibers.
- inorganic fibers include glass fibers, carbon fibers, metal fibers, ceramic fibers, and the like.
- organic fibers include aramid fibers, vinylon fibers, polyethylene fibers, and cellulose fibers.
- the fiber base material may contain glass fibers from the viewpoint of providing excellent reinforcing effects for the molded body.
- the fiber base material may contain inorganic fibers as a main component, and may be an inorganic fiber base material (for example, a glass fiber base material) consisting essentially of inorganic fibers.
- the glass composition of the glass fibers constituting the glass fiber base material is not particularly limited. SiO 2 in the range of 0% by weight, Al 2 O 3 in the range of 12.0-16.0% by weight, MgO and CaO in the range of 20.0-25.0% by weight in total, 5.0% by weight.
- B 2 O 3 in the range of ⁇ 10.0% by mass a high-strength, high-modulus glass composition (SiO 2 in the range of 60.0-70.0% by mass based on the total amount of glass fibers, Al 2 O 3 in the range of 20.0 to 30.0% by mass, MgO in the range of 5.0 to 15.0% by mass, Fe 2 O 3 in the range of 0 to 1.5% by mass, the total composition containing Na 2 O, K 2 O, and Li 2 O in the range of 0 to 0.2% by mass), and a high elastic modulus easily manufacturable glass composition (57.0 to 60% by mass based on the total amount of glass fibers).
- SiO 2 in the range of 60.0-70.0% by mass based on the total amount of glass fibers
- Al 2 O 3 in the range of 20.0 to 30.0% by mass MgO in the range of 5.0 to 15.0% by mass
- Fe 2 O 3 in the range of 0 to 1.5% by mass the total composition containing Na 2 O, K 2 O
- a low dielectric constant, low dielectric loss tangent glass composition (based on the total amount of glass fibers, SiO 2 in the range of 48.0 to 62.0 mass % and SiO 2 in the range of 17.0 to 26.0 mass %)
- B2O3 in the range Al2O3 in the range 9.0-18.0% by weight, CaO in the range 0.1-9.0% by weight , and CaO in the range 0-6.0% by weight.
- MgO a total of Na 2 O, K 2 O and Li 2 O in the range of 0.05 to 0.5 mass %, TiO 2 in the range of 0 to 5.0 mass %, and 0 to 6.0 mass %.
- a silane coupling agent may be attached to the surface of the fiber base material.
- the silane coupling agent include epoxysilane, aminosilane, acrylicsilane, methacrylsilane, and cationic silane.
- the epoxysilane include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.
- the mass A1 per unit area of the fiber base material is 30 g/m 2 or more, 50 g/m 2 or more, 100 g/m 2 or more, 150 g/m 2 or more, 180 g/m 2 from the viewpoint of easily securing sufficient strength. 200g/ m2 or more, 220g/ m2 or more, 250g/m2 or more, 300g/ m2 or more, 350g/ m2 or more, 400g/ m2 or more, 500g/ m2 or more, or 600g/ m2 It may be more than that.
- the mass A1 is 1000 g/m 2 or less, 900 g/m 2 or less, 800 g/m 2 or less, 700 g/m 2 or less, 600 g/m 2 or less, 500 g/m 2 or less, from the viewpoint of easily obtaining sufficient formability. , 400 g/m 2 or less, 350 g/m 2 or less, 300 g/m 2 or less, 250 g/m 2 or less, or 220 g/m 2 or less. From these points of view, the mass A1 may be 30 to 1000 g/m 2 , 150 to 800 g/m 2 , 180 to 600 g/m 2 , 200 to 500 g/m 2 , or 200 to 400 g/m 2 . The mass A1 tends to be the same before and after providing the resin portion on the fiber base material.
- the mass A1 per unit area of the fiber base material As a method for measuring the mass A1 per unit area of the fiber base material, when the fiber base material contains inorganic fibers, the resin part attached to the fiber base material was removed by heating (for example, heating at 625 ° C. for 1 hour). The mass of the subsequent fiber base material can be measured.
- the fiber base material contains organic fibers
- the mass A1 per unit area of the fiber base material can be measured by a known method. For example, when the fiber base material is a glass fiber fabric, the mass A1 per unit area of the fiber base material can be measured in accordance with JIS R 3420:2013.
- the content (content ratio) per unit area of the fiber base material is the total amount per unit area of the resin-attached fiber base material, or the total mass per unit area of the fiber base material and the resin part (mass A1 and mass A2 may be in the following range based on the sum of From the viewpoint of easily ensuring sufficient strength, the content per unit area of the fiber base material is more than 90.0 mass%, 90.5 mass% or more, 91.0 mass% or more, 92.0 mass% or more, It may be 93.0% by mass or more, 94.0% by mass or more, or 95.0% by mass or more.
- the content per unit area of the fiber base material is less than 100.0% by mass, and from the viewpoint of easily obtaining sufficient formability, it is 99.5% by mass or less, 99.0% by mass or less, 98.5% by mass % or less, 98.0 mass% or less, 97.5 mass% or less, 97.0 mass% or less, 96.5 mass% or less, 96.0 mass% or less, 95.0 mass% or less, 94.0 mass% It may be less than or equal to 93.0% by mass.
- the content per unit area of the fiber base material is more than 90.0 mass% and less than 100.0 mass%, 90.5 mass% or more and less than 100.0 mass%, 90.5 to 99.5 mass% % by weight, 91.0-99.0% by weight, or 95.0-98.0% by weight.
- the average structural unit width B1 of the fiber base material is 150 ⁇ m or more, 300 ⁇ m or more, 350 ⁇ m or more, 500 ⁇ m or more, 550 ⁇ m or more, 600 ⁇ m or more, 700 ⁇ m or more, 750 ⁇ m or more, 800 ⁇ m or more, 900 ⁇ m or more, from the viewpoint of easily ensuring sufficient strength. , 1000 ⁇ m or more, 1100 ⁇ m or more, 1200 ⁇ m or more, 1300 ⁇ m or more, 1350 ⁇ m or more, 1500 ⁇ m or more, 2000 ⁇ m or more, 2500 ⁇ m or more, 3000 ⁇ m or more, or 3500 ⁇ m or more.
- the average structural unit width B1 is 4500 ⁇ m or less, 4000 ⁇ m or less, 3500 ⁇ m or less, 3000 ⁇ m or less, 2500 ⁇ m or less, 2000 ⁇ m or less, 1500 ⁇ m or less, 1350 ⁇ m or less, 1300 ⁇ m or less, 1200 ⁇ m or less, 1100 ⁇ m or less, 1000 ⁇ m or less, 900 ⁇ m or less , 800 ⁇ m or less, 750 ⁇ m or less, or 700 ⁇ m or less.
- the average constituent unit width B1 may be 150 to 4500 ⁇ m, 350 to 3500 ⁇ m, 500 to 1500 ⁇ m, 550 to 1350 ⁇ m, or 600 to 1300 ⁇ m.
- the average structural unit width B1 tends to be the same before and after providing the resin portion on the fiber base material.
- the average value of the warp yarn width and the weft yarn width can be used as the average constituent unit width B1.
- the average value of the thread widths of the threads constituting each axis can be used as the average structural unit width B1.
- the fiber base material is a fiber knitted fabric
- the average value of the yarn widths of all types of knitting yarns included in the fiber knitted fabric can be used as the average constituent unit width B1.
- the average structural unit width B1 is determined by selecting 10 warps or wefts at approximately equal intervals from the entire width of the textile fabric in the weft direction or warp direction. , select 10 locations from the entire length of each warp or weft so that they are approximately equally spaced, and measure the thread width using a ruler or microscope (for example, KEYENCE Corporation, product name: VHX-2000, The average value of the warp or weft is determined based on the yarn widths of 6 locations, excluding the maximum 2 locations and the minimum 2 locations of the obtained thread widths (magnification: 200x). , can be obtained by calculating their average value.
- the yarn width herein means the maximum width in a cross section perpendicular to the longitudinal direction of the yarn, and does not include gaps between adjacent yarns.
- the filament diameter is, for example, 1.0 to 35.0 ⁇ m, 3.0 to 30.0 ⁇ m, 3.5 to 20.0 ⁇ m, 5.0 ⁇ m. ⁇ 10.0 ⁇ m, or 6.5 to 9.5 ⁇ m.
- the fineness of the thread which is a constituent unit of the fiber base material, is not particularly limited as long as the mass per unit area A1 and the average constituent unit width B1 can be achieved, but for example, 1 to 1500 tex (g/1000 m), It may be 1 to 1000 tex, 2 to 1000 tex, 5 to 800 tex, 10 to 700 tex, 20 to 500 tex, 30 to 300 tex, or 50 to 200 tex.
- the warp weave density and the weft weave density are not particularly limited as long as the mass per unit area A1 and the average constituent unit width B1 can be achieved, but each independently, 5 ⁇ 200 lines/25mm, 7-150 lines/25mm, 10-100 lines/25mm, or 15-50 lines/25mm. Further, the ratio of weft weave density to warp weave density (weft weave density/warp weave density) is 0.5 to 2.0, 0.6 to 1.7, 0.8 to 1.3, or 0. It may be between 9 and 1.1.
- the resin portion containing a thermoplastic resin is provided in a dot shape on at least one surface of the fiber base material.
- the resin portion may be attached to only one side of the fiber base material, or may be attached to both sides of the fiber base material.
- the resin part may be a thermoplastic resin part consisting essentially of a thermoplastic resin.
- "Dot-like" usually means that a plurality of circular (approximately circular (including perfect circles) or approximately elliptical) points are regularly arranged, but the shape or arrangement of each point is not particularly limited.
- the shape of each point may be a square, a hexagon, a star, or the like. Further, each point may be irregularly arranged.
- thermoplastic resins include polyamide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polycarbonate, polypropylene, thermoplastic epoxy resin, polyethylene, polyvinyl chloride, polyphenylene ether, polyether ether ketone, polyarylether ketone, and liquid crystal polymer (LCP). ) etc.
- Polyamide is a thermoplastic resin because it easily suppresses fiber fraying, facilitates the release of the resin material (matrix resin), provides excellent adhesion, and provides excellent flexibility.
- the content of polyamide is 50% by mass or more, more than 50% by mass, 70% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, based on the total amount of the resin part. It may be % by mass or more, or substantially 100% by mass (in an embodiment in which the resin portion is essentially made of polyamide).
- the melting point of the resin part or the melting point of the thermoplastic resin is 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 71°C or higher, 72°C or higher, or 75°C from the viewpoint of easily obtaining excellent processability.
- the temperature may be 78°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher.
- the melting point of the resin part or the melting point of the thermoplastic resin is 300°C or less, 250°C or less, 200°C or less, 150°C or less, 120°C or less, 110°C or less, 100°C
- the temperature may be below 95°C, below 90°C, below 80°C, below 78°C, or below 75°C.
- the melting point of the resin part or the melting point of the thermoplastic resin is 55 to 300°C, 55 to 150°C, 55 to 100°C, 55 to 95°C, 60 to 90°C, or 71 to 90°C. It may be.
- the melting point of the resin portion and the melting point of the thermoplastic resin can be measured in accordance with JIS K 7121:2012.
- the resin part may contain components other than thermoplastic resin.
- Such components include thermosetting resins, thickeners, surfactants, inorganic particles, lubricants, pigments, and the like.
- thermosetting resins include epoxy resins and urethane resins.
- Thickeners include inorganic compounds such as water-soluble alkali silicate, montmorillonite, and colloidal alumina; cellulose derivative compounds such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; pluronic polyether, polyether dialkyl ester, and polyether dialkyl.
- Polyether compounds such as ether, modified polyether urethane, and modified polyether epoxy; polyacrylic acid compounds such as sodium polyacrylate and polyacrylic acid (meth)acrylate copolymer; polyvinylpyrrolidone, polyvinyl alcohol , polyvinyl-based compounds such as polyvinylbenzyl alcohol copolymers; protein derivatives such as sodium caseinate and ammonium caseinate; partial esters of vinyl methyl ether-maleic anhydride copolymers, drying oil fatty acid allyl alcohol esters-maleic anhydride Examples include maleic anhydride copolymers such as half esters of reactants.
- surfactants include carboxylates, sulfonates, sulfuric ester salts, quaternary ammonium salts, amine salts, betaine types, polyhydric alcohol types, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxy Examples include ethylene polyoxypropylene glycol and polyethylene glycols.
- the inorganic particles include titanium oxide particles, zinc oxide particles, silicon dioxide particles, activated carbon particles, silver particles, and copper particles.
- paraffin wax synthetic polyethylene
- liquid paraffin liquid paraffin
- stearic acid behenic acid
- hydroxystearic acid stearyl alcohol
- stearamide oleic acid amide
- erucic acid amide methylene bis stearic acid amide
- ethylene bis stearic acid amide examples include glycerin monostearate, glycerin monooleate, butyl stearate, metal soap, and fumed silica.
- Pigments include alkali blue, Lysol red, carmine 6B, disazo yellow, phthalocyanine blue, quinacridone red, isoindoline yellow, red clay, ocher, green clay, malachite, chalk, graphite, navy blue, zinc white, cobalt blue, emerald green, Examples include viridian, titanium white, fluorescent pigments, metal powder pigments, pearl pigments, thermochromic pigments, and the like.
- the mass A2 per unit area of the resin part is 0.3 g/m 2 or more, 0.5 g/m 2 or more, 0.3 g/m 2 or more, 0.5 g/m 2 or more, from the viewpoint of easily suppressing fiber fraying and easily obtaining excellent adhesive properties.
- 8g/ m2 or more 1.0g/ m2 or more, 1.2g/m2 or more, 1.5g/ m2 or more, 2.0g/ m2 or more, 2.5g/ m2 or more, 3.0g/ m2 or more m2 or more, 3.5g/ m2 or more, 4.0g/ m2 or more, 4.5g/m2 or more, 5.0g/ m2 or more, 6.0g/ m2 or more, 8.0g/ m2 9.0 g/m 2 or more, 10.0 g/m 2 or more, 11.0 g/m 2 or more, 12.0 g/m 2 or more, 14.0 g/m 2 or more, 15.0 g/m 2 or more, 15.5 g/m 2 or more, 16.0 g/m 2 or more, 17.0 g/m 2 or more, 18.0 g/m 2 or more, 19.0 g/m 2 or more, 19.4 g/m 2 or more, or It may be 20.0 g/
- the mass A2 is set to 30.0 g/m 2 or less, 27.0 g/m 2 or less, and 25.0 g/m 2 or less, from the viewpoint of easily releasing the resin material (matrix resin) and obtaining excellent flexibility.
- m2 or less 22.0g/ m2 or less, 20.0g/ m2 or less, less than 20.0g/ m2 , 19.4g/ m2 or less, 19.0g/ m2 or less, 18.0g/ m2 Below, 17.0g/m 2 or less, 16.0g/m 2 or less, 15.5g/m 2 or less, 15.0g/m 2 or less, 14.0g/m 2 or less, 12.0g/m 2 or less, 11.0 g/m 2 or less, 10.0 g/m 2 or less, 9.0 g/m 2 or less, 8.0 g/m 2 or less, 6.0 g/m 2 or less, 5.0 g/m 2 or less, 4.
- the mass A2 is 0.3 to 30.0 g/m 2 , 1.0 to 19.4 g/m 2 , 3.5 to 15.5 g/m 2 , 4.0 to 15.0 g/m 2 m 2 , 5.0 to 15.0 g/m 2 , 5.0 to 12.0 g/m 2 , or 8.0 to 15.0 g/m 2 .
- the mass A2 is the total mass of the resin parts on both sides.
- the mass A2 per unit area of the resin part can be measured by the following procedure. First, 10 cm x 10 cm samples were cut out from five separate locations in the resin-attached fiber base material. Then, the mass of each sample obtained is measured. Next, each sample is immersed in a solvent that is soluble in the resin part, and the mass after dissolving the resin part is measured. Calculate the mass per unit area of each sample from the difference between the two obtained measurement values and the area of each sample, and exclude one sample where this value is the maximum and one sample where this value is the minimum. Let the average value of the mass per unit area of the three samples be the mass A2 per unit area of the resin part.
- the content (content ratio) per unit area of the resin part is the total amount per unit area of the resin-attached fiber base material, or the sum of the masses per unit area of the fiber base material and the resin part (mass A1 and mass A2). It may be in the following range based on the total).
- the content per unit area of the resin part is 9.5% by mass or less, 9.0% by mass or less from the viewpoint of facilitating the release of the resin material (matrix resin) and the viewpoint of easily obtaining excellent flexibility. , 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, or 5.0% by mass or less.
- the content per unit area of the resin part is 0.5% by mass or more, 1.0% by mass or more, and 1.5% by mass from the viewpoint of easily suppressing fiber fraying and easily obtaining excellent adhesive properties. % or more, 2.0 mass% or more, 2.5 mass% or more, 3.0 mass% or more, 3.5 mass% or more, 4.0 mass% or more, 5.0 mass% or more, 6.0 mass% or more, or 7.0% by mass or more. From these viewpoints, the content per unit area of the resin part is 0.5 to 9.5% by mass, 1.0 to 9.0% by mass, or 2.0 to 5.0% by mass. good.
- the average diameter B2 of the resin part is 20 ⁇ m or more, 50 ⁇ m or more, 70 ⁇ m or more, 75 ⁇ m or more, 80 ⁇ m or more, 100 ⁇ m or more, 150 ⁇ m or more, from the viewpoint of easily suppressing fiber fraying and easily obtaining excellent adhesive properties. It may be 200 ⁇ m or more, 250 ⁇ m or more, 300 ⁇ m or more, 350 ⁇ m or more, 400 ⁇ m or more, 450 ⁇ m or more, 500 ⁇ m or more, 550 ⁇ m or more, 600 ⁇ m or more, 650 ⁇ m or more, 700 ⁇ m or more, 750 ⁇ m or more, 750 ⁇ m or more, or 800 ⁇ m or more.
- the average diameter B2 is 2000 ⁇ m or less, 1500 ⁇ m or less, 1200 ⁇ m or less, 1000 ⁇ m or less, 800 ⁇ m or less, 700 ⁇ m or less, or 650 ⁇ m from the viewpoint of facilitating the release of the resin material (matrix resin) and from the viewpoint of easily obtaining excellent flexibility. Below, it may be 600 ⁇ m or less, 550 ⁇ m or less, 500 ⁇ m or less, 450 ⁇ m or less, 400 ⁇ m or less, 350 ⁇ m or less, 300 ⁇ m or less, 250 ⁇ m or less, 200 ⁇ m or less, 150 ⁇ m or less, less than 150 ⁇ m, or 100 ⁇ m or less. From these viewpoints, the average diameter B2 may be 20 to 2000 ⁇ m, 75 to 1200 ⁇ m, 100 to 650 ⁇ m, 150 to 550 ⁇ m, 150 to 450 ⁇ m, or 200 to 500 ⁇ m.
- the average diameter B2 of the resin portion can be obtained by observing the resin portion in the resin-attached fiber base material using a microscope and measuring the diameter of the resin portion. The diameters of 20 resin parts were measured while changing the measurement points so that the measurement points were approximately evenly distributed in the resin-attached fiber base material, and the diameters of 20 resin parts were measured, counting from the maximum and 5 from the minimum. The average value of the 10 measured values excluding 1 measured value can be obtained as the average diameter B2 of the resin portion. If the shape of the resin part is not a perfect circle, the area of the resin part can be measured using area calculation software built into the microscope, and the diameter of a perfect circle having the area can be obtained as the diameter of the resin part.
- the coverage rate of the resin part in the resin-attached fiber base material is less than 100.0%, and from the viewpoint of easy removal of the resin material (matrix resin) and the viewpoint of easy to obtain excellent flexibility, the coverage ratio of the resin part is 50.0%. % or less, less than 50.0%, 45.0% or less, 40.0% or less, 35.0% or less, 30.0% or less, less than 30.0%, 29.4% or less, 28.0% or less , 25.0% or less, 20.0% or less, 15.0% or less, 10.0% or less, 5.0% or less, 3.0% or less, or 2.0% or less.
- the coverage rate of the resin part is 0.1% or more, 0.5% or more, 1.0% or more, 2.0% from the viewpoint of easily suppressing fiber fraying and easily obtaining excellent adhesive properties. 3.0% or more, 5.0% or more, 10.0% or more, 15.0% or more, 20.0% or more, 25.0% or more, 28.0% or more, 29.4% or more, It may be 30.0% or more, or 35.0% or more. From these viewpoints, the coverage of the resin part is 0.1% or more and less than 100.0%, 0.1 to 50.0%, 0.1 to 45.0%, 0.5 to 35.0%, It may be 0.5% or more and less than 30.0%, 1.0 to 29.4%, or 2.0 to 20.0%.
- the coverage rate of the resin part is the ratio of the area of the part on the surface of the resin-attached fiber base material where the resin part is present (the part covered by the resin part on the surface of the resin-attached fiber base material).
- the coverage of the resin part is determined by observing the surface of the resin-attached fiber base material using a microscope, and calculating the area S1 of the entire surface of the resin-attached fiber base material (the area occupied by the fibers, which is the area of the voids existing between the fibers). (excluding area) and the area S2 of the portion where the resin portion is present on the surface of the resin-attached fiber base material can be obtained using the formula "(S2/S1) x 100".
- the coverage of the resin part is the average value of the coverage of one side and the other side.
- the total mass per unit area of the fiber base material and the resin portion may be in the following range. From the viewpoint of easily securing sufficient strength, the total mass is 30 g/m 2 or more, 50 g/m 2 or more, 100 g/m 2 or more, 150 g/m 2 or more, 180 g/m 2 or more, 200 g/m 2 or more , 220 g/m 2 or more, 250 g/m 2 or more, 300 g/m 2 or more, 350 g/m 2 or more, 400 g/m 2 or more, 500 g/m 2 or more, or 600 g/m 2 or more.
- the total mass is 1000 g/m 2 or less, 900 g/m 2 or less, 800 g/m 2 or less, 700 g/m 2 or less, 600 g/m 2 or less, 500 g/m 2 from the viewpoint of easily obtaining sufficient formability.
- it may be 400 g/m 2 or less, 350 g/m 2 or less, 300 g/m 2 or less, 250 g/m 2 or less, or 220 g/m 2 or less. From these points of view, the total mass may be 30 to 1000 g/m 2 , 150 to 800 g/m 2 , 180 to 600 g/m 2 , 200 to 500 g/m 2 , or 200 to 400 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin part to the mass A1 per unit area of the fiber base material is 0.005 to 0.105.
- the ratio A2/A1 is 0.005 or more, fraying of the fibers during cutting can be suppressed and sufficient adhesiveness can be obtained. It is presumed that the reason why such an effect is obtained is that sufficient resin is attached to the fiber base material when the ratio A2/A1 is 0.005 or more.
- the ratio A2/A1 is 0.105 or less, the resin material (matrix resin) can be easily removed when the resin material (matrix resin) is brought into contact.
- the ratio A2/A1 is 0.006 or more, 0.007 or more, 0.010 or more, 0.015 or more, 0.016 from the viewpoint of easily suppressing fiber fraying and easily obtaining excellent adhesive properties.
- the ratio A2/A1 is set to 0.100 or less, 0.080 or less, 0.077 or less, and 0.075 from the viewpoint of easily achieving good release of the resin material (matrix resin) and from the viewpoint of easily obtaining excellent flexibility.
- 0.070 or less, 0.063 or less, 0.062 or less, 0.060 or less, 0.050 or less, 0.049 or less, 0.048 or less, 0.040 or less, 0.035 or less, 0.030 below, it may be 0.025 or less, 0.021 or less, 0.020 or less, 0.016 or less, 0.015 or less, 0.010 or less, or 0.007 or less.
- the ratio A2/A1 is 0.006 to 0.080, 0.016 to 0.063, 0.016 to 0.062, 0.020 to 0.050, 0.030 to 0.050. , 0.040 to 0.050, 0.021 to 0.049, or 0.020 to 0.040.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average structural unit width B1 of the fiber base material is 0.06 to 0.96.
- the ratio B2/B1 is 0.06 or more, fraying of the fibers during cutting can be suppressed, and sufficient adhesiveness can be obtained.
- the reason why such an effect is obtained is that when the ratio B2/B1 is 0.06 or more, the resin part is appropriately dispersed and attached to the fiber base material, and the fibers can be sufficiently fixed. It is assumed that When the ratio B2/B1 is 0.96 or less, it is possible to improve the release of the resin material (matrix resin) when the resin material (matrix resin) is brought into contact with the resin material, and it is easy to obtain excellent flexibility.
- the ratio B2/B1 is 0.96 or less, so that the voids between the threads, the edges of the threads, etc. that make up the fiber base material are difficult to be excessively covered by the resin part. This is presumed to be because the resin material (matrix resin) is less likely to be prevented from passing through the voids.
- the factors for obtaining the above-mentioned effects are not limited to the above-mentioned contents.
- the ratio B2/B1 is 0.08 or more, 0.10 or more, 0.15 or more, 0.19 or more, 0.20 from the viewpoint of easily suppressing the fraying of the fibers and from the viewpoint of easily obtaining excellent adhesive properties. 0.22 or more, 0.24 or more, 0.25 or more, 0.30 or more, 0.33 or more, 0.35 or more, 0.38 or more, 0.40 or more, 0.45 or more, 0.50 It may be 0.60 or more, 0.65 or more, or 0.67 or more.
- the ratio B2/B1 is set to 0.95 or less, 0.90 or less, 0.80 or less, and 0.70 from the viewpoint of easily achieving good release of the resin material (matrix resin) and from the viewpoint of easily obtaining excellent flexibility.
- the ratio B2/B1 is 0.06 to 0.90, 0.06 to 0.70, 0.15 to 0.60, 0.19 to 0.50, 0.20 to 0.50. , 0.20 to 0.49, 0.22 to 0.45, 0.24 to 0.38, 0.26 to 0.38, or 0.30 to 0.50.
- the resin-attached fiber base material according to the present embodiment may have a ratio A2/A1 of 0.016 to 0.062 and a ratio B2/B1 of 0.20 to 0.50.
- a molded body is obtained using the resin-attached fiber base material according to this embodiment.
- a molded body may be obtained using the laminate having the resin-attached fiber base material according to this embodiment.
- the laminate may be a laminate obtained by laminating a plurality of resin-attached fiber base materials according to the present embodiment, and may be a laminate obtained by laminating a plurality of resin-attached fiber base materials according to the present embodiment (one or more resin-attached fiber base materials). It may be a laminate obtained by laminating the base material and another base material.
- Such other base materials include metal foil (aluminum foil, etc.), thermoplastic resin sheet (vinyl chloride resin sheet, etc.), mineral wool sheet (glass wool sheet, etc.), inorganic board (gypsum board, ceramic board, etc.), Examples include paper (noncombustible paper, honeycomb board, etc.).
- the method for producing a molded article according to the present embodiment includes forming a molded article using various molding methods using the resin-attached fiber base material according to the present embodiment (which may be the resin-attached fiber base material in the above-mentioned laminate).
- a process may be provided.
- a molded body may be obtained by RTM molding using the resin-attached fiber base material according to this embodiment.
- a molded body may be obtained by bringing a resin material (matrix resin) into contact with the resin-attached fiber base material according to this embodiment, and a resin material (matrix resin) may be brought into contact with the resin-attached fiber base material according to this embodiment.
- a molded article may be obtained by infiltrating the material.
- a resin material (matrix resin) may be brought into contact (for example, permeated) with the resin-attached fiber base material in the mold.
- the resin material include epoxy resin, phenol resin, acrylic resin, polyamide, polyolefin, polyester (for example, unsaturated polyester resin), polyurethane, polyvinylidene chloride, polyvinyl chloride, and the like.
- the molded object may be obtained through a plurality of steps, and the following step may be provided before the molding step.
- the method for producing a molded article according to the present embodiment may include a step of laminating a plurality of resin-attached fiber base materials according to the present embodiment to obtain a laminate, and the method may include a step of laminating a plurality of resin-attached fiber base materials according to the present embodiment to obtain a laminate.
- the method may include a step of laminating a plurality of resin-attached fiber base materials) and another base material to obtain a laminate.
- the method for manufacturing a molded article according to this embodiment may include a step of cutting the resin-attached fiber base material according to this embodiment (which may be the resin-attached fiber base material in the above-mentioned laminate).
- the method for manufacturing a molded article according to this embodiment may include a step of heating and pressurizing the resin-attached fiber base material according to this embodiment (which may be the resin-attached fiber base material in the above-mentioned laminate).
- the molded article according to this embodiment is a molded article obtained by the method for producing a molded article according to this embodiment.
- the shape of the molded body is not particularly limited.
- the molded article according to the present embodiment may include the resin-attached fiber base material according to the present embodiment, and may include a base material obtained by melting the resin portion of the resin-attached fiber base material according to the present embodiment. .
- the molded article according to this embodiment can be used as various parts of automobiles, airplanes, transportation equipment, machines, structures, etc., for example.
- Example 1 ⁇ Preparation of resin-attached fiber base material> (Example 1) First, by using glass fiber yarn (E glass composition, glass filament diameter: 9.0 ⁇ m, fineness: 135 tex) as the warp and weft, weaving at a weaving density of 19 warps/25 mm and 18 wefts/25 mm. (Weave structure: plain weave) was obtained. Next, this woven fabric is subjected to a heat cleaning treatment and an opening treatment using a vibro washer, and then surface treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxy silane) to remove glass fibers. A woven fabric (fiber base material) was obtained.
- glass fiber yarn E glass composition, glass filament diameter: 9.0 ⁇ m, fineness: 135 tex
- Weave structure plain weave
- this woven fabric is subjected to a heat cleaning treatment and an opening treatment using a vibro washer, and then surface treated with 3-glycidoxypropyltrimethoxysilane (
- the mass A1 (mass measured in accordance with JIS R 3420:2013; the same applies hereinafter) per unit area of the glass fiber fabric is 209 g/ m2
- the average constituent unit width B1 of the glass fiber fabric is 209 g/m2.
- the measured average value of the warp width and the weft width was 1200 ⁇ m.
- polyamide manufactured by M Chemie Co., Ltd., trade name: D1666AP1, melting point measured in accordance with JIS K 7121:2012: 75°C
- polyamide manufactured by M Chemie Co., Ltd., trade name: D1666AP1, melting point measured in accordance with JIS K 7121:2012: 75°C
- D1666AP1 melting point measured in accordance with JIS K 7121:2012: 75°C
- a screen having dot-shaped openings dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 40 pieces per 1 inch (2.54 cm) square) were evenly provided, and then The resin part was fixed by heating. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 29.4%.
- the mass A2 per unit area of the resin portion was 10.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.048.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- the average diameter B2 and coverage rate of the resin portion were measured using a microscope (manufactured by Keyence Corporation, trade name: VHS-8000) (the same applies hereinafter).
- Example 2 First, by using glass fiber yarn (E glass composition, glass filament diameter: 9.0 ⁇ m, fineness: 135 tex) as the warp and weft, weaving at a weaving density of 19 warps/25 mm and 18 wefts/25 mm. (Weave structure: plain weave) was obtained. Next, this woven fabric was subjected to a heat cleaning treatment and then surface treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxy silane) to obtain a glass fiber woven fabric (fiber base material). . The mass A1 per unit area of the glass fiber fabric was 209 g/m 2 , and the average constituent unit width B1 of the glass fiber fabric was 700 ⁇ m.
- E glass composition glass filament diameter: 9.0 ⁇ m, fineness: 135 tex
- Example 2 the same type of polyamide as in Example 1 was attached to the surface of the above-mentioned glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 200 ⁇ m, 30 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 4.4%. The mass A2 per unit area of the resin portion was 5.0 g/m 2 .
- dot-shaped resin parts circular, average diameter B2: 200 ⁇ m, 30 pieces per square inch
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.024.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.29.
- Example 3 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 10 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 1.9%. The mass A2 per unit area of the resin portion was 1.5 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin part to the mass A1 per unit area of the glass fiber fabric was 0.007.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- Example 4 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 40 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 29.4%. The mass A2 per unit area of the resin portion was 16.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin part to the mass A1 per unit area of the glass fiber fabric was 0.077.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- Example 5 First, by using glass fiber yarn (E glass composition, glass filament diameter: 9.0 ⁇ m, fineness: 100 tex) as the warp and weft, weaving at a weaving density of 30 warps/25 mm and 30 wefts/25 mm. (Weave structure: plain weave) was obtained. Next, this woven fabric is subjected to a heat cleaning treatment and an opening treatment using a vibro washer, and then surface treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxy silane) to remove glass fibers. A woven fabric (fiber base material) was obtained. The mass A1 per unit area of the glass fiber fabric was 335 g/m 2 , and the average constituent unit width B1 of the glass fiber fabric was 750 ⁇ m.
- E glass composition glass filament diameter: 9.0 ⁇ m, fineness: 100 tex
- Example 2 the same type of polyamide as in Example 1 was attached to the surface of the above-mentioned glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular shape, average diameter B2: 500 ⁇ m, 30 pieces per square inch) are evenly provided, and then the resin is heated. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 27.0%. The mass A2 per unit area of the resin portion was 15.0 g/m 2 .
- dot-shaped resin parts circular shape, average diameter B2: 500 ⁇ m, 30 pieces per square inch
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.045.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.67.
- Example 6 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 800 ⁇ m, 20 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 29.4%. The mass A2 per unit area of the resin portion was 10.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.048.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.67.
- Example 7 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 100 ⁇ m, 50 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 3.0%. The mass A2 per unit area of the resin portion was 10.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.048.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.08.
- Example 8 First, by using glass fiber yarn (E glass composition, glass filament diameter: 9.0 ⁇ m, fineness: 1100 tex) as the warp and weft at a weaving density of 8 warps/25 mm and 8 wefts/25 mm, a fabric is fabricated. (Weave structure: plain weave) was obtained. Next, this woven fabric is subjected to a heat cleaning treatment and an opening treatment using a vibro washer, and then surface treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxy silane) to remove glass fibers. A woven fabric (fiber base material) was obtained. The mass A1 per unit area of the glass fiber fabric was 625 g/m 2 , and the average constituent unit width B1 of the glass fiber fabric was 3500 ⁇ m.
- E glass composition glass filament diameter: 9.0 ⁇ m, fineness: 1100 tex
- Example 2 the same type of polyamide as in Example 1 was attached to the surface of the above-mentioned glass fiber fabric. Specifically, using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 45 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 39.0%. The mass A2 per unit area of the resin portion was 20.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.032.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.11.
- Example 9 A resin-attached fiber base material was prepared in the same manner as in Example 1, except that the type of polyamide was changed to "2APO77" (trade name, manufactured by M Chemie Co., Ltd.) (melting point measured in accordance with JIS K 7121:2012: 120°C). I got it.
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.048.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- a glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 5 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage rate of the resin portion was 0.5%. The mass A2 per unit area of the resin portion was 0.5 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.002.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- Example 2 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 400 ⁇ m, 50 pieces per square inch) are evenly provided, and then heated to form resin parts. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 50.0%. The mass A2 per unit area of the resin portion was 28.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin part to the mass A1 per unit area of the glass fiber fabric was 0.134.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.33.
- Example 3 A glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular, average diameter B2: 1500 ⁇ m, 10 pieces per square inch) are evenly provided, and then the resin is heated. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 27.0%. The mass A2 per unit area of the resin portion was 18.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.086.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 1.25.
- a glass fiber fabric (fiber base material) was obtained by the same procedure as in Example 1. Next, the same type of polyamide as in Example 1 was attached to the surface of this glass fiber fabric. Specifically, by using a screen with dot-shaped openings, dot-shaped resin parts (circular shape, average diameter B2: 50 ⁇ m, 55 pieces per square inch) are evenly provided, and then the resin is heated. The part was fixed. Subsequently, by cooling to room temperature, a resin-attached fiber base material having dot-shaped resin portions provided on one side of the glass fiber fabric was obtained. In the resin-attached fiber base material, the coverage of the resin portion was 0.9%. The mass A2 per unit area of the resin portion was 5.0 g/m 2 .
- the ratio A2/A1 of the mass A2 per unit area of the resin portion to the mass A1 per unit area of the glass fiber fabric was 0.024.
- the ratio B2/B1 of the average diameter B2 of the resin portion to the average constituent unit width B1 of the glass fiber fabric was 0.04.
- a base material piece was obtained by cutting the resin-attached fiber base material described above into a 10 cm square. After obtaining a laminate A by laminating 10 of these base material pieces, a laminate B is obtained by sandwiching this laminate A between two release films (manufactured by Panac Co., Ltd., product name: SP PET7501BU). Obtained. Subsequently, a 30 cm square glass plate weighing 1 g was placed on the laminate B, and then heated at 100° C. for 60 minutes. After cooling for 1 hour at room temperature, the degree of adhesion between the base material pieces was evaluated. The case where all the base materials are adhered to each other is evaluated as "A”, the case where some of the base materials are peeled off is evaluated as "B”, and the case where all the base materials are peeled off is evaluated as " It was rated "C”.
- a base material piece was obtained by cutting the resin-attached fiber base material described above into a 10 cm square. This piece of base material was immersed in 100 mL of matrix resin (unsaturated polyester resin, manufactured by Showa Denko Co., Ltd., product name: RIGOLAC 158BQTN-1) for 5 minutes, and then pulled out. The amount of change in mass of the resin-attached fiber base material before and after dipping was determined. Using the same procedure, the penetration amount M2 of the matrix resin was also determined for the above-mentioned glass fiber fabric (fiber base material) in which no resin portion was provided.
- matrix resin unsaturated polyester resin, manufactured by Showa Denko Co., Ltd., product name: RIGOLAC 158BQTN-1
- the omission of the matrix resin was evaluated based on the ratio of the amount of penetration M1 to the amount of penetration M2, "(M1/M2) x 100".
- the ratio is 80% or more, it is evaluated as “A”, when the ratio is 60% or more and less than 80%, it is evaluated as “B”, and when the ratio is less than 60%, it is evaluated as "C”. .
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Abstract
Description
[1]繊維基材と、当該繊維基材の少なくとも一方の面に設けられたドット状の樹脂部と、を備え、前記樹脂部が熱可塑性樹脂を含有し、前記繊維基材の単位面積当たりの質量A1に対する前記樹脂部の単位面積当たりの質量A2の比率A2/A1が0.005~0.105であり、前記繊維基材の平均構成単位幅B1に対する前記樹脂部の平均径B2の比率B2/B1が0.06~0.96である、樹脂付着繊維基材。
[2]前記比率A2/A1が0.016~0.062であり、前記比率B2/B1が0.20~0.50である、[1]に記載の樹脂付着繊維基材。
[3]前記樹脂部の融点が55~95℃である、[1]又は[2]に記載の樹脂付着繊維基材。
[4][1]~[3]のいずれか一つに記載の樹脂付着繊維基材を加熱加圧する工程を備える、成形体の製造方法。
(実施例1)
まず、ガラス繊維糸(Eガラス組成、ガラスフィラメント径:9.0μm、繊度:135tex)を経糸及び緯糸として用いて、経糸19本/25mm及び緯糸18本/25mmの織密度で製織することにより織物(織組織:平織)を得た。次に、この織物に対して、ヒートクリーニング処理、及び、バイブロウォッシャーによる開繊処理を施した後、3-グリシドキシプロピルトリメトキシシラン(エポキシシランの一種)で表面処理を行うことによりガラス繊維織物(繊維基材)を得た。ガラス繊維織物の単位面積当たりの質量A1(JIS R 3420:2013に準拠して測定される質量;以下同様)は209g/m2であり、ガラス繊維織物の平均構成単位幅B1(上述の方法で測定される、経糸の糸幅と緯糸の糸幅との平均値;以下同様)は1200μmであった。
まず、ガラス繊維糸(Eガラス組成、ガラスフィラメント径:9.0μm、繊度:135tex)を経糸及び緯糸として用いて、経糸19本/25mm及び緯糸18本/25mmの織密度で製織することにより織物(織組織:平織)を得た。次に、この織物に対して、ヒートクリーニング処理を施した後、3-グリシドキシプロピルトリメトキシシラン(エポキシシランの一種)で表面処理を行うことによりガラス繊維織物(繊維基材)を得た。ガラス繊維織物の単位面積当たりの質量A1は209g/m2であり、ガラス繊維織物の平均構成単位幅B1は700μmであった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:400μm、1インチ角当たり10個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、1.9%であった。樹脂部の単位面積当たりの質量A2は、1.5g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.007であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.33であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:400μm、1インチ角当たり40個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、29.4%であった。樹脂部の単位面積当たりの質量A2は、16.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.077であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.33であった。
まず、ガラス繊維糸(Eガラス組成、ガラスフィラメント径:9.0μm、繊度:100tex)を経糸及び緯糸として用いて、経糸30本/25mm及び緯糸30本/25mmの織密度で製織することにより織物(織組織:平織)を得た。次に、この織物に対して、ヒートクリーニング処理、及び、バイブロウォッシャーによる開繊処理を施した後、3-グリシドキシプロピルトリメトキシシラン(エポキシシランの一種)で表面処理を行うことによりガラス繊維織物(繊維基材)を得た。ガラス繊維織物の単位面積当たりの質量A1は335g/m2であり、ガラス繊維織物の平均構成単位幅B1は750μmであった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:800μm、1インチ角当たり20個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、29.4%であった。樹脂部の単位面積当たりの質量A2は、10.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.048であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.67であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:100μm、1インチ角当たり50個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、3.0%であった。樹脂部の単位面積当たりの質量A2は、10.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.048であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.08であった。
まず、ガラス繊維糸(Eガラス組成、ガラスフィラメント径:9.0μm、繊度:1100tex)を経糸及び緯糸として用いて、経糸8本/25mm及び緯糸8本/25mmの織密度で製織することにより織物(織組織:平織)を得た。次に、この織物に対して、ヒートクリーニング処理、及び、バイブロウォッシャーによる開繊処理を施した後、3-グリシドキシプロピルトリメトキシシラン(エポキシシランの一種)で表面処理を行うことによりガラス繊維織物(繊維基材)を得た。ガラス繊維織物の単位面積当たりの質量A1は625g/m2であり、ガラス繊維織物の平均構成単位幅B1は3500μmであった。
ポリアミドの種類をエムスケミー社製の商品名「2APO77」(JIS K 7121:2012に準拠して測定される融点:120℃)に変更したこと以外は実施例1と同様の手順により樹脂付着繊維基材を得た。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.048であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.33であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:400μm、1インチ角当たり5個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、0.5%であった。樹脂部の単位面積当たりの質量A2は、0.5g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.002であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.33であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:400μm、1インチ角当たり50個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、50.0%であった。樹脂部の単位面積当たりの質量A2は、28.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.134であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.33であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:1500μm、1インチ角当たり10個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、27.0%であった。樹脂部の単位面積当たりの質量A2は、18.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.086であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は1.25であった。
実施例1と同様の手順によりガラス繊維織物(繊維基材)を得た。次に、このガラス繊維織物の表面に実施例1と同一種のポリアミドを付着させた。具体的には、ドット状の開口を有するスクリーンを用いて、ドット状の樹脂部(円状、平均径B2:50μm、1インチ角当たり55個)を均等に設けた後、加熱することで樹脂部を固着させた。続いて、常温まで放冷することにより、ガラス繊維織物の一方面に設けられたドット状の樹脂部を備える樹脂付着繊維基材を得た。樹脂付着繊維基材において、樹脂部の被覆率は、0.9%であった。樹脂部の単位面積当たりの質量A2は、5.0g/m2であった。ガラス繊維織物の単位面積当たりの質量A1に対する樹脂部の単位面積当たりの質量A2の比率A2/A1は0.024であった。ガラス繊維織物の平均構成単位幅B1に対する樹脂部の平均径B2の比率B2/B1は0.04であった。
上述の樹脂付着繊維基材を用いて下記の評価を行った。結果を表1に示す。
30cm角以上のサイズの上述の樹脂付着繊維基材を10cm角に裁断し、裁断時に裁断面から落下した繊維を集めた。その繊維の質量を測定し、裁断前の樹脂付着繊維基材の質量に対する、裁断面から落下した繊維の質量の割合を算出した。割合が3%以下である場合を「A」と評価し、割合が3%超5%未満である場合を「B」と評価し、割合が5%以上である場合を「C」と評価した。
上述の樹脂付着繊維基材を10cm角にカットすることにより基材片を得た。この基材片10枚を積層することにより積層体Aを得た後、この積層体Aを2枚の離型フィルム(パナック株式会社製、商品名:SP PET7501BU)で挟むことにより積層体Bを得た。続いて、30cm角、1gのガラス板を積層体Bに載せた後、100℃で60分加熱した。そして、常温で1時間放冷後、基材片同士の接着の程度を評価した。各基材同士が全て接着されている場合を「A」と評価し、基材の一部が剥離していた場合を「B」と評価し、基材の全てが剥離していた場合を「C」と評価した。
上述の樹脂付着繊維基材を10cm角にカットすることにより基材片を得た。この基材片を100mLのマトリックス樹脂(不飽和ポリエステル樹脂、昭和電工株式会社製、商品名:リゴラック 158BQTN-1)に5分間浸漬させた後に引き上げ、樹脂付着繊維基材に対するマトリックス樹脂の浸透量M1として、浸漬前後の樹脂付着繊維基材の質量の変化量を求めた。同様の手順により、樹脂部を設けていない上述のガラス繊維織物(繊維基材)についてもマトリックス樹脂の浸透量M2を求めた。浸透量M2に対する浸透量M1の割合「(M1/M2)×100」に基づき、マトリックス樹脂の抜けを評価した。割合が80%以上である場合を「A」と評価し、割合が60%以上80%未満である場合を「B」と評価し、割合が60%未満である場合を「C」と評価した。
上述の樹脂付着繊維基材を手で触った感触を評価した。樹脂部を設けていない上述のガラス繊維織物(繊維基材)の感触と比較した。ガラス繊維織物と同程度の感触である場合を「A」と評価し、ガラス繊維織物より硬いが許容範囲である場合を「B」と評価し、ガラス繊維織物より硬く許容範囲し得ない場合を「C」と評価した。
Claims (4)
- 繊維基材と、当該繊維基材の少なくとも一方の面に設けられたドット状の樹脂部と、を備え、
前記樹脂部が熱可塑性樹脂を含有し、
前記繊維基材の単位面積当たりの質量A1に対する前記樹脂部の単位面積当たりの質量A2の比率A2/A1が0.005~0.105であり、
前記繊維基材の平均構成単位幅B1に対する前記樹脂部の平均径B2の比率B2/B1が0.06~0.96である、樹脂付着繊維基材。 - 前記比率A2/A1が0.016~0.062であり、前記比率B2/B1が0.20~0.50である、請求項1に記載の樹脂付着繊維基材。
- 前記樹脂部の融点が55~95℃である、請求項1に記載の樹脂付着繊維基材。
- 請求項1~3のいずれか一項に記載の樹脂付着繊維基材を加熱加圧する工程を備える、成形体の製造方法。
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Citations (4)
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WO2003004758A1 (fr) * | 2001-07-04 | 2003-01-16 | Toray Industries, Inc. | Materiau de base renforce par fibres de carbone, preforme et materiau composite renfermant ledit materiau |
JP2006103305A (ja) * | 2004-09-10 | 2006-04-20 | Toray Ind Inc | プリフォーム用基材 |
JP2018066074A (ja) * | 2016-10-17 | 2018-04-26 | 株式会社Shindo | 一方向性強化繊維シート |
WO2018150978A1 (ja) | 2017-02-17 | 2018-08-23 | 日東紡績株式会社 | 樹脂付着強化繊維織物、及び繊維強化樹脂成形品の製造方法 |
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WO2003004758A1 (fr) * | 2001-07-04 | 2003-01-16 | Toray Industries, Inc. | Materiau de base renforce par fibres de carbone, preforme et materiau composite renfermant ledit materiau |
JP2006103305A (ja) * | 2004-09-10 | 2006-04-20 | Toray Ind Inc | プリフォーム用基材 |
JP2018066074A (ja) * | 2016-10-17 | 2018-04-26 | 株式会社Shindo | 一方向性強化繊維シート |
WO2018150978A1 (ja) | 2017-02-17 | 2018-08-23 | 日東紡績株式会社 | 樹脂付着強化繊維織物、及び繊維強化樹脂成形品の製造方法 |
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